DE3840373A1 - Thermoplastic, fibre-reinforced composite material comprising polyphenylene ethers and polyamides - Google Patents

Abstract

Thermoplastic, fibre-reinforced composite materials obtainable by impregnating reinforcing fibres with the melt of polyphenylene ethers, polyamides, a low-molecular-weight organic acid amide and optionally a styrene polymer, and process for their preparation, and their use.

Description

The invention relates to thermoplastic fiber-reinforced composites that by impregnating reinforcing fibers with a melt of polyphenylene ethers, Polyamides and low molecular weight organic acid amides available are.

Fiber-reinforced, thermoplastic composite materials, such as those made of DE-OS 37 24 155 based on a polypropylene matrix are known valuable construction materials, especially in machine and apparatus construction, as well as in the automotive and aircraft industries. Their relatively low temperature resistance represents a certain disadvantage. On the other hand, the Use of high temperature resistant plastics as a matrix especially on Due to their poor flow properties, it is very difficult and inadequate possible. From US 33 79 792, EP-A 2 21 341 and EP-A 2 25 170 for example, unreinforced, high-temperature resistant molding compounds based on known from polyphenylene ethers, in which the flow properties by addition of polyamides could be improved. At the same time, however other important properties of polyphenylene ethers, for example mechanical Properties, deteriorated.

The object of the present invention was therefore fiber-reinforced composite materials based on polyphenylene ethers and polyamides with good mechanical and thermal properties.

Surprisingly, it was found that such composite materials with the required good mechanical and thermal properties, as well as with good Processability can be obtained if the polyphenylene ether used Polyamide mixture of low molecular weight organic acid amides. The invention accordingly relates to a thermoplastic fiber-reinforced Composite material made by impregnating reinforcing fibers with the Melt a mixture of 10 to 90 parts by weight of polyphenylene ether and 90 to 10 parts by weight of polyamide is available, the mixture additionally 0.1 to 10% by weight, based on the amount of polyamide, a low molecular weight organic  Contains acid amides and the polyphenylene ether optionally up to 50 wt .-% can be replaced by a thermoplastic styrene polymer.

Composite materials are preferred which are made by impregnating the reinforcing fibers by hot pressing at temperatures from 200 to 350 ° C and pressing 1.2 to 40 bar are available.

The mixture for impregnating the reinforcing fibers preferably contains 40 to 60 parts by weight of polyphenylene ether and 60 to 40 parts by weight of polyamide.

Examples of suitable polyphenylene ethers and polyamides are those such as in US 33 79 792, EP-A 2 21 341 or EP-A 2 25 170 are preferred are poly (2,6-dialkyl-1,4-phenylene) ether with 1 or 2 carbon atoms in the alkyl radical as well as polyamide 6 or polyamide 6.6. Other examples of polyamides (PA) are poly-4-aminobutyric acid (PA 4), poly-7-aminoheptanoic acid (PA 7), Poly-8-aminooctanoic acid (PA 8), poly-10-aminodecanoic acid (PA 10), poly-11- aminoundecanoic acid (PA 11), poly-12-aminododecanoic acid (PA 12), polyheptamethylene pimelamide (PA 7.7), polyoctamethylene suberamide (PA 8.8), polyhexamethylene sebacamide (PA 6.10), polynonamethylene acelamide (PA 9.9), polydecamethylene acelamide (PA 10.9), polydecamethylene sebacamide (PA 10.10), polybis (4- aminocyclohexyl) methane 1.10 decanedicarboxamide, poly (m-xylylene adipamide), Poly (p-xylylenesebacamide), polypiperazine sebacamide.

The polyphenylene ether used can contain up to 50% by weight of conventional homo- and copolymers of styrene, for example polystyrene, polymethylstyrene or be replaced by rubber-modified styrene polymers. Polymer blends of polyphenylene ethers and polyamides are, for example, as Ultranyl® (BASF), Noryl® GTX (General Electric), Prevex® (Borg Warner) or Xyron® (Asahi), polymer blends made from polyphenylene ethers and modified polystyrene for example as Luranyl® (BASF) or Noryl® 110 (General Electric) commercially available.

Low molecular weight organic acid amides include both aliphatic and also aromatic acid amides containing one or more amide groups can and are optionally substituted to understand. Aliphatic are preferred  Acid amides with 3 to 18 carbon atoms and aromatic acid amides with 7 to 14 carbon atoms. For example, sebacic acid amide, oleic acid amide, succinic acid diamide, Adipic acid diamide, anthranilic acid amide, stearinamide, Benzamide, malonic acid diamide, pimelic acid diamide, glutaric acid diamide, corkic acid diamide, Azelaic acid diamide and phthalic acid diamide can be used. The Polymer mixture for impregnating the reinforcing fibers preferably contains 0.5 to 5% acid amide based on the amount of polyamide.

All known reinforcing fibers are suitable for reinforced plastics usable fibers such. B. fibers of glass, carbon, aramid, ceramic, metal or mixtures thereof. Among fibers are both cut fibers as well To understand continuous fibers, for example in the form of unidirectional rovings, as well as fabrics and fiber mats, which are also made of cut fibers or Continuous fibers can exist. The finished composite usually has one Reinforcing fiber content of about 15 to 60% by volume.

The composite materials according to the invention are produced by impregnation of the reinforcing fibers at 200 to 350 ° C with the melt one Mixture of 10 to 90 parts by weight of polyphenylene ether and 90 to 10 parts by weight Polyamide, the mixture additionally 0.1 to 10 wt .-%, based on the Amount of the polyamide, a low molecular weight organic acid amide contains and the polyphenylene ether optionally up to 50 wt .-% by a thermoplastic Styrene polymer can be replaced. The thermoplastic mixture can adhesion promoters are also added, for example block copolymers Polyamides and polyphenylene ethers, such as z. B. in J. Pol. Sci., Pol. Chem. Ed. 17 (1979) pp. 2317-2335.

For example, fiber mats, fabrics or rovings made from continuous fibers be impregnated by pultrusion. In the case of rovings you can do this either individual roving strands or several strands placed side by side Roving strands pulled through the melt and after calibration then cooled to solidify.

In a preferred method, the reinforcing fibers are impregnated by pressing together with the melt in a hot press  Temperatures from 200 to 350 ° C and pressures from 1.2 to 40 bar. Especially it is preferred to use a continuous press which presses the mixture of polyphenylene ethers, polyamide, acid amide and optionally styrene polymer either in the form of a pre-made film or as freshly extruded Melt together with a fiber mat, tissue or unidirectional Roving strands are fed. After impregnation in the hot lamination zone the press is cooled in a subsequent cooling zone and Solidification of the bond also under pressure. It is also possible to use cut fibers with the powdered, the acid amide to mix containing polymer mixture, then in an extruder melt and extrude as a strand. Continuous fiber roving strands can be in an extrusion tool that simultaneously melts and rovings are fed, are extruded as a fiber-reinforced polymer strand.

After cooling, the fiber-reinforced polymer strands can become granules are cut, for example, by injection molding or extrusion Finished parts can be processed further. The in the form of webs or Boards of existing composite materials can be used as a starting material for manufacture of molded parts can be used by hot pressing. The around 200 Sheets or sheets heated up to 350 ° C are turned into heated molds inserted and at temperatures of about 50 to 100 ° C and pressures of 1 to 100 bar pressed.

Comparative Example V1

A polymer blend of 55% by weight polyphenylene ether (PPE) and 45% by weight polyamide 6 (PA), corresponding to Ultranyl® KR 4510 (BASF), was in an extruder melted at 290 ° C, using a slot die as a 1.3 m wide film extruded with a basis weight of 3033 g / m² and a double belt press with 5 m / min speed fed. At the same time, the double belt press a needled glass mat each above and below the melt film Cut fibers with a basis weight of 650 g / m² each (Syncomat, Fa. Syncoglas, Belgium). At a temperature of 250 ° C in the heating zone and 80 ° C in the cooling zone, and a line pressure of 5 bar was a 3.3 mm thick, 1.3 m wide, glass fiber reinforced web with a glass content of 30% by weight and a basis weight of 4333 g / m². The melt index (MFI) of the polymer blend (measured after extrusion according to DIN 53 735 in g / 10 min at 280 ° C and 5 kg load, nozzle diameter 2.2 mm) as well as tensile strength (DIN 53 455), elongation (DIN 53 455), impact resistance (DIN 53 453), flexural modulus of elasticity (DIN 53 457), heat resistance (DIN 53 461, method B) and water absorption (DIN 16 918, 48 h) of the finished composite are summarized in Table 1.

Examples 2-5

Analogously to Example V1, glass fiber-reinforced webs were made from a polymer blend obtained from polyphenylene ether and polyamide, with the difference that the polymer blend before extrusion in each case 2% by weight, based on the amount of Polyamids, the following acid amides listed in Table 1 admixed were: anthranilic acid amide (AN), adipic acid diamide (AD), oleic acid amide (OA), Succinic acid diamide (BA). Melt index, as well as mechanical and thermal Properties are summarized in Table 1.

Comparative Example V6

A mixture of 50% by weight of a mixture of 60% polyphenylene ether and 40% Polystyrene, corresponding to Noryl 110 from General Electric, and 50% by weight Polyamide 6, corresponding to Ultramid B 4 from BASF, was from an extruder  Wide slot die extruded at 280 ° C. The melt film (basis weight 3000 g / m²) was continuously on a double belt press at 250 ° C and 5 bar with 2 Glass mats (Syncomat, each 650 g / m²) pressed. After the discharge from the In the cooling zone, a glass fiber-reinforced web of 3.2 mm thickness was obtained Basis weight of 4300 g / m² and a glass content of 30% by weight. The The melt index of the mixture and the properties of the composite are shown in the table 1 compiled.

Examples 7 and 8

Analogous to example V6, glass fiber reinforced composite webs made of polyphenylene ether, Polystyrene and polyamide are made, however, before extrusion in Example 7 2% by weight (based on the amount of the polyamide) Adipic acid diamide (AD), and in example 8 2% by weight succinic acid diamide (BA) was added. The melt index after extrusion and the properties the compounds are shown in Table 1.  

Table 1

Composite of polyphenylene ether and polyamide with 30% by weight glass fiber

Claims (10)

1. Thermoplastic fiber reinforced composite, available through Impregnation of reinforcing fibers with the melt of a mixture 10 to 90 parts by weight of polyphenylene ether and 90 to 10 parts by weight of polyamide, wherein the mixture additionally 0.1 to 10 wt .-%, based on the amount of Polyamids, a low molecular weight organic acid amide contains and Polyphenylene ether optionally up to 50 wt .-% by a thermoplastic Styrene polymer can be replaced. 2. Composite material according to claim 1, obtainable by impregnating Reinforcing fibers with the mixture of polyphenylene ether, polyamide, low molecular weight organic acid amide and optionally styrene polymers by hot pressing at temperatures from 200 to 350 ° C and pressures from 1.2 to 40 bar. 3. Composite material according to claim 1 or 2, characterized in that the Mixture for impregnating the reinforcing fibers 0.5 to 5% acid amide, based on the amount of polyamide. 4. Composite material according to one of claims 1 to 3, characterized in that that the low molecular weight organic acid amides are aliphatic acid amides with 3 to 18 C-atoms or aromatic acid amides with 7 to 14 C- Atoms. 5. Composite material according to one of claims 1 to 4, characterized in that the mixture for impregnating the reinforcing fibers 40 to 60 Parts by weight of polyphenylene ether and 60 to 40 parts by weight of polyamide. 6. Process for the production of thermoplastic fiber reinforced composites according to claim 1, characterized in that reinforcing fibers with the melt of a mixture of 10 to 90 parts by weight of polyphenylene ether and 90 to 10 parts by weight of polyamide at temperatures of 200 are impregnated up to 350 ° C, the mixture additionally 0.1 to 10 wt .-%, based on the amount of polyamide, a low molecular weight  contains organic acid amides and the polyphenylene ether optionally up to 50% by weight can be replaced by a thermoplastic styrene polymer can. 7. A method for producing composite materials according to claim 6, characterized characterized in that the impregnation by pressing together of reinforcing fibers with the mixture of polyphenylene ether, polyamide, Acid amide and optionally styrene polymers at temperatures of 200 up to 350 ° C and pressures from 1.2 to 40 bar. 8. A method for producing composite materials according to claim 7, characterized characterized in that the mixture of polyphenylene ether, polyamide, Acid amide and optionally styrene polymers in the form of a prefabricated Film or a freshly extruded melt film is used and together with the reinforcing fibers, which are in the form of a mat or in Form of unidirectional continuous fiber strands, a continuous Press are fed. 9. Use of composite materials according to one of claims 1 to 5 as Starting material for the production of molded parts by hot pressing. 10. Use of composite materials according to one of claims 1 to 5 as Starting material for the production of granules.