WO2009095440A1

WO2009095440A1 - Transparent polyamide[5,10] molding compounds

Info

Publication number: WO2009095440A1
Application number: PCT/EP2009/051006
Authority: WO
Inventors: Motonori Yamamoto; Weol Kyu Jeong; Arnold Schneller; Rolf-Egbert GRÜTZNER; Freddy Gruber; Jürgen Deininger
Original assignee: Basf Se
Priority date: 2008-01-31
Filing date: 2009-01-29
Publication date: 2009-08-06

Abstract

The invention relates to transparent polyamide[5,10] molding compounds having a transmittance, measured according to ASTM D1003 on 1 mm thick, injection-molded plates, of greater than or equal to 80% and to a method and to master batches for producing said molding compounds. The invention further relates to the use of said molding compounds for producing any type of molded article and to the molded articles thereby obtainable, preferably any body component of a motor vehicle or electronic components, films and fibers.

Description

Transparent polyamide [5,10] molding compounds

description

The present invention relates to polyamide [5,10] molding compositions having a transmission measured according to ASTM D1003 on 1 mm thick, injection-molded plates of greater than or equal to 80% and in particular comprising polyamide [5,10] molding compositions

A) 0.001 to 5% by weight of a nucleating agent,

B) 0 to 60 wt .-% fibrous fillers

C) 0 to 30% by weight of further additives,

wherein the sum of the weight percentages of polyamide [5,10] and components A) to C) is 100%.

Moreover, the present invention relates to a method and masterbatches for producing such molding compositions, the use of such molding compositions for the production of moldings of any kind and the moldings obtainable in this case, preferably automotive body parts of any kind or electronic components, films and fibers.

From WO2007 / 113127 a process for the preparation of pentamethylenediamine and its polycondensation with aliphatic dicarboxylic acids to give polyamides is known. About polyamide [5,10] is little known in the literature. Commercially available polyamides such as polyamide [6] or polyamide [6,10] can not always be completely satisfactory in terms of their transparency.

The aim of the present invention was to increase the transparency of polyamides without impairing the mechanical properties.

Surprisingly, the polyamides [5, 10] according to the invention have a significantly higher transparency than comparable polyamide [6] and polyamide [6,10] molding compounds. In particular, this property occurs in the case of molding compositions having a nucleating agent content of from 0.001 to 5% by weight; At the same time, the mechanical properties such as impact resistance are also improved.

The polyamides [5, 10] can be prepared as described in WO 2007/113127. In the molding compositions according to the invention, the polyamides [5, 10] in the fiber-reinforced case are generally in a proportion of from 40 to 96, preferably 45 to 92 and in particular 50 to 91% by weight and in the non-fiber-reinforced case usually in a proportion of 70 to 99.9, preferably 95 to 99.8 and in particular 97 to 99.8 wt .-%.

As component A) molding compositions according to the invention preferably sodium or calcium phenylphosphinate, calcium fluoride, finely divided polytetrafluoroethylene, polyamide [2,2], polyamide [4,6], boron compounds, alumina, silica or talc. Particularly preferred are talc and polyamide [2,2].

Talc, which [(OH) 2 / Si4θio] 3 or MgO ^■ is a hydrated magnesium silicate having the composition Mg 3 SiO 2 4 ^■ H 2 O, being particularly preferred. These so-called three-layer phyllosilicates have a triclinic, monoclinic or rhombic crystal structure with a platelet-like appearance. On further trace elements Mn, Ti, Cr, Ni, Na and K may be present, wherein the OH group may be partially replaced by fluoride.

Particular preference is given to the use of talc, the particle size of which is 99.5%.

<20 microns. The particle size distribution is usually determined by sedimentation analysis DIN 6616-1 and is preferably:

<20 μm 99.5% by weight

<10 μm 99% by weight

<5 μm 85% by weight

<3 μm 60% by weight

<2 μm 43% by weight

Such products are commercially available as Micro-Tale I.T. extra (Omya) available.

The nucleating agents A) are used in a concentration of 0.001 to 5, preferably 0.01 to 1, 0 and particularly preferably 0.05 to 0.2 wt .-%.

As fiber-containing fillers B) carbon fibers, glass fibers, called, in amounts of 1 to 60 wt .-%, in particular from 10 to 50, preferably from 20 to 40 wt .-% are used.

Preferred fibrous fillers are glass fibers, carbon fibers, aramid fibers, potassium titanate fibers and natural fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or in particular as chopped glass in the commercial forms. The fibers generally have a diameter of 3 to 30 microns, preferably 6 to 20 microns and more preferably from 8 to 15 microns. The fiber length in the compound is generally 20 .mu.m to 1000 .mu.m, preferably 180 to 500 .mu.m and more preferably 200 to 400 .mu.m. Natural fibers are understood as meaning cellulose fibers, hemp fibers, sisal or kenaf.

For better compatibility with the thermoplastic, the fibrous fillers can be surface-pretreated with a silane compound.

Suitable silane compounds are those of the general formula

(X- (CH 2) n) k -Si - (O-CmH 2m + 1) 4-k

in which the substituents have the following meanings:

X is NH ₂ -, CH ₂ -CH-, HO-,

\ /

O n is an integer from 2 to 10, preferably 3 to 4 m, an integer from 1 to 5, preferably 1 to 2 k, an integer from 1 to 3, preferably 1

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.

The silane compounds are generally used in amounts of from 0.01 to 2, preferably from 0.025 to 1, 0 and in particular from 0.05 to 0.5% by weight (based on C) of the surface coating.

Suitable additives C) are also acicular mineral fillers C). In the context of the invention, the term "needle-shaped mineral fillers" is understood to mean a mineral filler with a pronounced, needle-like character. An example is acicular wollastonite. Preferably, the mineral has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 1: 1: 1. The mineral filler may optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not essential.

Other particulate fillers C) which may be mentioned are kaolin, calcined kaolin, wollastonite and chalk, and additionally platelet or needle-shaped fillers, preferably in amounts of between 0.1 and 20% by weight. Boehmite, bentonite, montmorillonite, vermicullite, hectorite, laponite, powdered quartz, mica, feldspar, calcium silicate and magnesium carbonate are preferably used for this purpose. However, dyes such as nigrosine and pigments such as titanium dioxide, zinc sulfide, ultramarine blue, iron oxide, anthraquinones, quinacridones, phthalocyanines, perylenes or mixtures thereof have proven to be suitable fillers. Particular preference is given to using nanofillers. According to the invention, an electrically conductive additive can be added as component C). Preferably, only one electrically conductive additive is used, but if appropriate two or more electrically conductive additives can also be used. Suitable electrically conductive additives are, for example, carbon nanotubes, graphite or conductive carbon black.

Carbon nanotubes in the context of the present invention are carbon-containing macromolecules in which the carbon has (mainly) graphite structure and the individual graphite layers are arranged in a tubular manner. Nanotubes and their synthesis are already known in the literature (for example J. Hu et al., Acc. Chem. Res. 32 (1999), 435-445). In principle, any type of nanotube can be used in the context of the present invention.

Preferably, the diameter of the individual tubular graphite layers (graphite tubes) is 4 to 12 nm, in particular 5 to 10 nm. Nanotubes can be divided into so-called single-walled nanotubes (SWNTs) and multiwalled nanotubes (MWNTs). differ. Thus, in the MWNTs, several graphite tubes are superposed on each other.

Furthermore, the outer shape of the tubes may vary, this may have uniform diameter inside and outside, but there are also knot-shaped tubes and worm-like structures (vermicular) produced.

The aspect ratio (length of the respective graphite tube to its diameter) is at least> 10, preferably> 5. The nanotubes have a length of at least 10 nm. In the context of the present invention, MWNTs are preferred as component E). In particular, the MWNTs have an aspect ratio of about 1000: 1 and an average length of about 10,000 nm.

The BET specific surface area is generally from 50 to 2000 m ² / g, preferably from 200 to 1200 m ² / g. The resulting in the catalytic preparation impurities (eg metal oxides) are generally according to HRTEM from 0.1 to 12%, preferably from 0.2 to 10%.

Suitable nanotubes can be obtained under the name "multiwaH" from Hyperion Catalysis Int., Cambridge MA (USA) (see also EP 205 556, EP 969 128, EP 270 666, US Pat. No. 6,844,061).

As Leitruß any conventional form of carbon black can be used, suitable, for example, the commercial product Ketjenblack 300 Akzo. Conductivity can also be used for conductivity modification. Due to graphitic layers embedded in amorphous carbon, soot conducts electrons (F. Camona, Ann. Chim., Fr., 13, 395 (1988)). The power line takes place within the aggregates of soot particles and between the aggregates, if the distances between the aggregates are small enough. In order to achieve conductivity with the lowest possible dosage, preference is given to using carbon blacks with anisotropic structure (G. Wehner, Advances in Plastics Technology, APT 2005, Paper 1, Katowice 2005). With such carbon blacks, the primary particles combine to form anisotropic structures, so that the distances of the soot particles necessary for achieving conductivity in compounds are achieved even at comparatively low loading (C. Van Bellingen, N. Probst, E. Grivei, Advances in Plastics Technology , APT 2005, Paper 13, Katowice 2005).

Suitable types of carbon black include, for example, an oil absorption (measured according to ASTM D 2414-01) of at least 60 ml / 100 g, preferably more than 90 ml / 100 g. The BET surface area of suitable products is more than 50, preferably more than 60 m ² / g (measured according to ASTM D 3037-89). There may be various functional groups on the carbon black surface. The Leitruße can be prepared by various methods (G. Wehner, Advances in Plastics Technology, APT 2005, Paper 1 1, Katowice 2005).

Furthermore, graphite can also be used as a conductivity additive. Graphite is a modification of the carbon as described, for example, in AF Hollemann, E. Wieberg, N. Wieberg, "Lehrbuch der anorganischen Chemie," 91.-100th ed., Pp. 701-702 Graphite can be comminuted by milling The particle size is in the range of 0.01 μm to 1 mm, preferably in the range of 1 to 250 μm.

The transparency of the mixtures according to the invention can be increased in many cases by adding 0.05 to 1.0% by weight of a phosphorus compound of the general structure

[RO- (R'O) -P-Ar-] ₂

wherein R and R 'are independently a C _r C ₈ alkyl, C _r C ₈ -Alkoky, aryl or substituted with C _r C ₆ -alkyl aryl group and Ar represents a 1, 4-phenylene, 1, 3-phenylene , 2,6-naphthylene, 2,7-naphthylene or a 4,4'-diphenylene radical or their Ci-Ce-alkyl-substituted derivatives mean are added. A preferred phosphorus compound is commercially available under the designation Irgafos® P-EPQ (Ciba-Geigy). As component C) it is possible to use further additives, such as stabilizers, oxidation inhibitors, flame retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants, such as dyes, plasticizers, etc.

Examples of flame retardants are red phosphorus, magnesium hydroxide and melamine cyanurate.

The stabilizers can be added to the polyamide [5,10] molding compositions at any stage in the preparation, but are preferably added as early as possible to prevent decomposition from starting already before the stabilizer is incorporated.

As examples of antioxidants and heat stabilizers, halides of metals of Group I of the Periodic Table, e.g. Sodium, potassium, and / or lithium halides, optionally in combination with copper (I) halides, e.g. Chlorides, bromides, iodides, hindered phenols, hydroquinones, various substituted representatives of these groups and mixtures thereof in concentrations up to 1 wt .-%, based on the weight of the thermoplastic molding compositions called.

UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition, of various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned.

Lubricants and mold release agents are usually used in quantities of max. 1 wt .-%, based on the total weight of the molding composition added. Examples of these are stearic acid, sterol alcohol and stearic acid amides.

With regard to minerals and fillers, the proportion of component C) in the novel molding materials is from 0 to 30% by weight, preferably from 1 to 15% by weight, particularly preferably from 1 to 5% by weight, based on the total weight the molding compound. The proportion of component C) in the molding compositions according to the invention is from 0 to 10% by weight, preferably from 0.05 to 2% by weight, and particularly preferably from 0.08 to 1% by weight, with regard to stabilizer and lubricant.

The polyamide [5,10] molding compositions according to the invention can preferably be prepared in a three-stage process (steps i) to Ni)) by means of so-called masterbatches containing 5 to 15% by weight nucleating agent:

i) 1, 5-pentamethylenediamine prepared by fermentation with Corynebacterium glutamicum, and sebacic acid, which can be prepared as described, for example, in US 2217515, are polycondensed; ii) the resulting polyamide [5.10] with 5 to 15 wt .-% nucleating agent in an extruder is compounded and iii) the masterbatch thus obtained with more polyamide [5,10] to the desired

Concentration of nucleating agent is discontinued.

Polyamide [5,10] can be prepared by polycondensation of 1, 5 pentamethylenediamine and sebacic acid in a molar ratio of 0.95: 1, 05 to 1, 05: 0.95 by known methods. The condensation can either be carried out batchwise in a batch process or else continuously. In a batchwise preparation of the polyamides, for example, an aqueous solution of the monomers is introduced in an autoclave and heated to generally 240 to 300 ^° C. A pressure of from 10 to 50 or rather 15 to 30 bar is established By relaxing excess water vapor can be kept constant for up to 4 hours. The heating phase (up to the desired reaction temperature) usually takes 0.5 to 3 hours. The stirring time, during which the reaction mixture is maintained at 240 to 300 ⁰ C, is usually 1 to 5 hours. Subsequently, it is depressurized to normal pressure during a period of 0.5 to 3 hours. The autoclave discharge is granulated, for example in a water bath. The continuous procedure can be carried out analogously to EP129195 or 129196.

The masterbatches and the molding compositions according to the invention can be prepared by processes known per se, by mixing the components polyamide [5.10], A) and, if appropriate, B) and C), in the melt at elevated temperatures or else by mixing Components in mixing devices. It is expedient to use extruders for this purpose, for example single-screw or twin-screw extruders or other conventional plasticizing devices, such as Brabender mills or Banbury mixers. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed. The mixing temperatures are usually 230 to 320 ⁰ C.

The molecular weight (Mn) of the polyamides [5, 10] according to the invention is preferably in the range from 1000 to 100000, in particular in the range from 9000 to 75000 and particularly preferably in the range from 10 000 to 50 000 g / mol.

The molding compositions according to the invention have, in particular, excellent transparency or, in certain mixtures, a surprisingly high translucency. The transmission was determined on a 1-mm-thick, injection-molded plate according to ASTM D1003 (MT / FT). The ASTM D1003 defines the total transmission as the ratio of transmitted light to incident light - measured in percent. The injection molding conditions for the production of plates: melting temperature of 260 ⁰ C, Mold temperature of 60 ⁰ C. The measurements were carried out on the device haze-gard plus from BYKGardner.

According to this method, the polyamide [5,10] molding compounds show a transmission of over 80%. Comparable literature known polyamides have a significantly lower transmission. Through the addition of nucleating agents, the transmission can be increased to over 90% according to ASTM D1003.

The molding compositions according to the invention are further distinguished by good notched impact toughness, improved flowability and surprisingly high ductility at -30 ^0C. In addition, the molding compositions according to the invention have a higher heat resistance (HDT B).

These are suitable for the production of fibers, films and moldings of any kind, especially for automotive and electronics applications. The following are some examples: Cylinder head covers, motorcycle covers, intake manifolds, intercooler caps, connectors, gears, fan wheels, cooling water boxes.

Inside the car, there is use for dashboards, steering column switches, seat parts, headrests, center consoles, transmission components and door modules, in the car exterior door handles, exterior mirror components, windscreen wiper components, windscreen wiper housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake manifolds , Windscreen wipers and bodywork exterior parts such as fenders, door trim, tailgates, spoilers, side panels, roof modules and hoods.

Suitable electronic components are e.g. Cell phone cases, laptop components, touch screen frames, navigator screen frames, calculator components, etc.

The molding compositions according to the invention are suitable for the production of spectacle frames and spectacle lenses.

Due to the high transparency, the molding compositions according to the invention are also suitable for the production of films, for example for the packaging of foods. In particular, films which have 0.01 to 1% by weight of polyamide [2.2] or, in particular, talc, have proved suitable here. Examples

Production and testing of molding compounds

The molecular weight Mn of the polymers is determined as follows:

15 mg of the polymers were dissolved in 10 ml of hexafluoroisopropanol (HFIP). Each 125 μl of this solution was analyzed by gel permeation chromatography (GPC). The measurements were carried out at room temperature. For the elution, HFIP + 0.05 wt% trifluoroacetic acid potassium salt was used. The elution rate was 0.5 ml / min. The following column combination was used (all columns manufactured by Showa Denko Ltd., Japan): Shodex® HFIP-800P (diameter 8 mm, length 5 cm), Shodex® HFIP-803 (diameter 8 mm, length 30 cm), Shodex ® HFIP-803 (diameter 8mm, length 30cm). The polymers were detected by means of a RI detector (differential refractometry). The calibration was carried out with narrowly distributed polymethyl methacrylate standards with molecular weights of Mn = 505 to Mn = 2,740,000. Elution areas outside this interval were determined by extrapolation.

The viscosity number of the polyamides was measured according to EN ISO 1628-1 on 0.5% strength by weight solutions in 96% by weight sulfuric acid. The polymers generally have a VZ of 10 to 400 ml / g, preferably 30 to 300 and particularly preferably 50 to 250 ml / g.

The MVR was measured according to ISO1133 (275 ° C, 5 kg load). The polyamides according to the invention have an MVR of 5 to 500 ml / 10 min, preferably 10 to 400, particularly preferably 20 to 300.

The transmission was determined on a 1 mm thick plate according to ASTM D1003. The measurements were performed on the haze-gard plus instrument by BYKGardner. The injection molding conditions for the production of plates: melting temperature of 260 ⁰ C, mold temperature of 60 ⁰ C.

Melting point measured according to DSC (DIN EN ISO 11357) PA [5,10] = 215 ° C.

The impact strength was determined according to ISO179-2.

The heat resistance of the samples was determined according to ISO 75-2 (HDT B) (load 0.45 MPa, temperature increase of 50 K per hour, on ISO rods). Preparation of 1, 5-pentanediamine

1, 5 Pentylenediamine was prepared by fermentation with Corynebacterium glutamicum (see WO2007 / 113127).

Production of polyamides

Polyamide [5,10] - Example 1

12.5 kg of aqueous 48.19% pentamethylenediamine solution, 12.2 kg of sebacic acid and 6.59 kg of distilled water were placed in a stirred tank. The reaction mixture was purged 10 times well with nitrogen and heated to 200 ⁰ C. This temperature and a pressure of 17 bar was kept constant for 1 hour. The pressure was then released to atmospheric pressure and the reaction mixture heated to 270 ⁰ C. Under nitrogen, the polymerization was continued at this temperature for 70 min. The polymer thus obtained has a VZ (viscosity number) of 151 ml / g according to EN ISO 1628-1.

Polyamide [6,10] - Comparative Example 2

In a stirred tank, 10.11 g of aqueous 69.0% hexamethylenediamine solution, 12.20 kg of sebacic acid and 16.04 kg of distilled water were added. The reaction mixture was purged well with nitrogen 10 times and heated to 200 ° C. The pressure was kept constant at this temperature at 17 bar for 1 hour. The reaction vessel was then expanded to atmospheric pressure and the reaction mixture heated to 270 ⁰ C. The polymer thus obtained has a VZ (viscosity number) of 154 ml / g according to EN ISO 1628-1.

Polyamide [6] - Comparative Example 3

Ultramid® B3 from BASF SE (VZ 151 ml / g) was used.

Component A

Talc IT-Extra from Omya. X10 = 1.7 μm. X90 = 10.8 microns (measured by laser diffraction, wherein the minerals were homogenized in a suspension cell in a deionized water / 1% CV K8 surfactant mixture (distributor: CV-Chemievertrieb, Hannover) (magnetic stirrer, 60 rpm). Production of masterbatch and compounding

On a twin-screw extruder ZSK25, 10% talc IT extra was compounded in polyamide [5,10]. The reaction temperature was 260 ⁰ C, speed 200UPM and the throughput 5kg / h.

This masterbatch concentrate was treated with additional polyamide [5,10] in a ZSK25 to obtain the desired concentration (0.1%) of talc.

In this way were prepared:

Example 4: PA [5.10] (Example 1) and 0.1% talc IT extra were compounded.

Comparative Example 5: PA [6,10] (Comparative Example 2) and 0.1% talc IT extra were compounded.

Comparative Example 6: PA 6 (Comparative Example 3) and 0.1% talc IT extra were compounded.

The polyamides according to the invention (Examples 1 and 4) have, in comparison to commercially available polyamides [6, 10] and [6], a high transmission according to ASTM D1003, with simultaneously good impact strength (ISO 179-2) and heat resistance (ISO75-2).

Claims

claims

1. Polyamide [5,10] molding compound with a transmission measured according to ASTM D1003 on 1 mm thick, injection-molded plates of greater than or equal to 80%.

2. Polyamide [5,10] -formmasse containing

A) 0.001 to 5% by weight of a nucleating agent,

B) 0 to 60 wt .-% fibrous fillers

C) 0 to 30% by weight of further additives,

where the sum of the weight percentages of polyamide [5.10] and components A) to C) is 100%.

3. polyamide [5,10] molding compositions according to claim 1, containing as component A) sodium or Calciumphenylphosphinat, calcium fluoride, finely divided polytetrafluoroethylene, polyamide [2,2], boron compounds, alumina, silica or talc.

4. polyamide [5,10] molding compositions according to claim 2, comprising as component A) 0.01 to 1 wt .-% talc or polyamide [2,2].

5. polyamide [5,10] molding compositions according to claim 1, containing as component B) chopped glass fiber or rovings.

6. polyamide [5,10] molding compositions according to claim 1, containing as component C) Carbonnanotubes, carbon black, graphite, nigrosine, titanium dioxide, zinc sulfide, ultramarine blue, iron oxide, anthraquinones, quinacridones, phthalocyanines, perylenes or mixtures thereof.

7. A process for the preparation of polyamide [5,10] molding compositions according to claim 1 to 3, characterized in that i) 1, 5-pentamethylenediamine, prepared by fermentation with Corynebacterium glutamicum, and sebacic acid - prepared from castor oil - are polycondensed ; ii) the resulting polyamide [5,10] is compounded with 5 to 15% by weight of nucleating agent in an extruder and iii) the masterbatch thus obtained is adjusted to the desired concentration of nucleating agent with further polyamide [5,10].

8. Masterbatch containing i) 85 to 95 wt .-% polyamide [5,10] and ii) 5 to 15 wt .-% nucleating agent.

9. Use of the polyamide [5,10] molding compositions according to one of claims 1 to 6 for the production of moldings in the automotive industry and in electronics.

10. fibers, films, moldings, obtainable from polyamide [5,10] molding compositions according to claims 1 to 6.

1 1. A film obtainable from polyamide [5,10] molding compositions according to claim 3.