POLYAMIDE COMPOSITIONS HAVING A HIGH MODULUS AND A LOW DIELECTRIC CONSTANT AND USE THEREOF

Abstract

A mixture of solid and hollow glass reinforcers with an alloy of at least one polyamide and of at least one polyolefin, the mixture of solid and hollow glass reinforcers including from 5% to 60% by weight of hollow glass beads relative to the sum of the solid and hollow glass reinforcers, the alloy-mixture proportions being from more than 50% to 75% of said mixture of solid and hollow glass reinforcers, to prepare a composition having a modulus, when dry at 20° C., of from 5 GPa to less than 8 GPa as measured according to ASTM D-2520-13, at a frequency of at least 1 GHz, at 23° C., under 50% RH.

Claims

1. A use of a mixture of solid and hollow glass reinforcers with an alloy consisting of at least one polyamide and at least one polyolefin, said mixture of solid and hollow glass reinforcers comprising from 5 to 60% by weight of hollow glass beads relative to the total of the solid and hollow glass reinforcers, the alloy-mixture proportions being greater than 50% to 75%, by weight of said solid and hollow glass reinforcer mixture, excluding polyamide 6 and 66, to prepare a composition having a modulus, when dry at 20° C., comprised from 5 GPa to less than 8 GPa, and a dielectric constant Dk, less than or equal to 3.1 as measured according to ASTM D-2520-13, at a frequency of at least 1 GHz, at 23° C., under 50% RH, said modulus corresponding either to the flexural modulus or to the tensile modulus, the flexural modulus being measured according to standard ISO 178:2010 and the tensile modulus (or modulus of elasticity E) being measured according to standard ISO 527-1 and 2:2012.

2. The use according to claim 1, wherein the dielectric loss (tan delta) of said composition is less than or equal to 0.01, as measured on a dry sample, at 23° C., under 50% RH, at a frequency of at least 1 GHz according to ASTM D-2520-13.

3. The use according to claim 1, wherein said mixture of solid and hollow glass reinforcers, in addition to hollow glass beads, comprises solid glass fibers selected from circular cross-section glass fibers, flat cross-section glass fibers and a mixture thereof.

4. The use according to claim 3, wherein the mixture of glass reinforcers consists of 40 to 95% by weight of solid glass fibers and from 5 to 60% by weight of hollow glass beads.

5. The use according to claim 1, wherein said alloy consists of at least one polyamide and at least one polyolefin, the polyamide/polyolefin weight ratio of which is between 95/5 and 50/50.

6. The use according to claim 1, wherein said at least one polyolefin is selected from grafted polyolefins and non-grafted polyolefins and a mixture thereof.

7. The use according to claim 6, wherein the reactive units of the grafted polyolefin are selected from esters of unsaturated carboxylic acids; vinyl esters of saturated carboxylic acids.

8. The use according to claim 6, wherein the grafted polyolefin is propylene-based.

9. The use according to claim 6, wherein the ungrafted polyolefin is selected from ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene and 1-triacontene.

10. The use according to claim 6, wherein the ungrafted polyolefin is propylene-based.

11. The use according to claim 5, wherein said alloy consists of at least one polyamide and a mixture of a polypropylene-based grafted polyolefin and a polypropylene-based non-grafted polyolefin.

12. The use according to claim 1, wherein said at least one polyamide is selected from semi-crystalline polyamides, amorphous polyamides and a mixture thereof.

13. The use according to claim 1, wherein said alloy consists of a single polyamide which is an amorphous polyamide and at least one polyolefin.

14. The use according to claim 13, wherein said amorphous polyamide is a polyamide of formula A/XY, wherein: A is an aliphatic repeating unit obtained by polycondensation: of at least one C.sub.6 to C.sub.18 amino acid, or of at least one C.sub.6 to C.sub.18 lactam, or of at least one C.sub.4-C.sub.36 dicarboxylic acid Cb; XY is an aliphatic repeating unit obtained by polycondensation: of at least one cycloaliphatic diamine, or at least one linear or branched aliphatic diamine X and of at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y.

15. The use according to claim 13 or 14, wherein said amorphous polyamide is selected from 11/B10, 12/B10, 11/BI/BT, 11/BI.

16. The use according to claim 1, wherein said alloy consists of a single semi-crystalline polyamide or a mixture of two semi-crystalline polyamides and at least one polyolefin.

17. The use according to claim 16, wherein the semi-crystalline polyamide is selected from aliphatic polyamides, aryl-aliphatic polyamides and semi-aromatic polyamides.

18. The use according to claim 16, wherein said polyamide mixture is a mixture of an aliphatic polyamide with an aryl-aliphatic polyamide.

19. The use according to claim 17, wherein the aliphatic polyamide is selected from PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA 12.

20. The use according to claim 17 or 18, wherein the aryl-aliphatic polyamide is selected from MXD6, MXD10, MXD12.

21. The use according to claim 17, wherein the semi-aromatic polyamide is selected from PA11/9T, PA11/10T, PA 11/12T, PA12/9T, PA12/10T, PA12/12T.

22. The use according to claim 11, wherein said alloy consists of a single polyamide which is an amorphous polyamide, and of a mixture of a polypropylene-based grafted polyolefin and a polypropylene-based non-grafted polyolefin.

23. The use according to claim 11, wherein said alloy consists of a mixture of two semi-crystalline polyamides and of a mixture of a polypropylene-based grafted polyolefin and a polypropylene-based non-grafted polyolefin.

24. The use according to claim 1, wherein the composition comprises additives.

25. The use according to claim 1, wherein the composition comprises at least one prepolymer.

26. A composition comprising: over 50 to 75% by weight of an alloy consisting of at least one polyamide and at least one polyolefin, as defined in claim 1, the polyamide/polyolefin ratio being comprised from 95:5 to 50:50; 25 to less than 50% by weight of a solid and hollow glass reinforcer mixture; excluding polyamide 6 and 66, and 0 to 11% by weight of at least one prepolymer, polyamide oligomers with a lower number average molecular weight than that of polyamides; 0 to 5% by weight of fillers, and 0 to 2% by weight of additives, the sum of the proportions of each constituent of said composition being equal to 100%.

27. The use of a composition as defined in claim 1, for the manufacture of an article for telecom applications or for data exchange.

28. The use according to claim 27, wherein the article is manufactured by injection molding.

29. An article obtained by injection molding with a composition as defined in claim 1.

Description

EXAMPLES

[0295] The present invention will now be illustrated in greater detail by means of the following examples without being in any way limited to these.

[0296] The various polyamides and copolyamides of the invention were prepared according to the usual techniques for polyamide and copolyamide synthesis.

[0297] Synthesis of CoPa 11/10T, representative of the various copolyamides: the aminoundecanoic, decanediamine and terephthalic acid monomers are loaded together in the reactor according to the desired mass ratio. The medium is first inerted to remove the oxygen that can generate yellowing or secondary reactions. Water can also be charged to improve heat exchange. Two temperature rise and pressure plateaus are conducted. The temperature)(T° and pressure conditions are selected to allow the medium to melt. After having reached the maintenance conditions, degassing takes place to allow the polycondensation reaction. The medium becomes viscous little by little and the reaction water formed is caused the nitrogen purge or applying a vacuum.

[0298] When the stoppage conditions are reached, related to the desired viscosity, stirring is stopped and the extrusion and granulation can start.

[0299] The compositions in Table 1 were prepared (% by weight) according to the following general protocol:

Compounding for the Preparation of the Granules of Said Formulations:

[0300] Twin screw extruder, such as Coperion ZSK 26 MC, with at least 1 lateral raw material inlet

Machine temperature: 270° C.
Screw speed: 250 rpm
Extruder output: 16 kg/h

Transformation:

[0301] Wafers 100×100×2 mm3 were made by injection molding for the measurements of the dielectric properties. The following parameters were used: [0302] ENGEL VICTORY 500, 160T hydraulic press [0303] Injection temperature (feed/nozzle): 265° C./280° C. [0304] Mold temperature: 100 C [0305] Holding time: 10 s [0306] Material holding pressure: 700 bar [0307] Cooling time: 35 s

[0308] Dumbbell-shaped specimens according to ISO 527-2 1A were produced by injection molding for the measurement of tensile mechanical properties. The following parameters were used: [0309] ENGEL VICTORY 500, 160T hydraulic press [0310] Injection temperature (feed/nozzle): 285° C./295° C. [0311] Mold temperature: 100 C [0312] Holding time: 10 s [0313] Material holding pressure: 700 bar [0314] Cooling time: 15 s

[0315] The results obtained from the compositions of the invention are shown in the following Table 1:

TABLE-US-00001 TABLE 1 C1 I1 I2 I3 I4 I5 I6 I7 I8 PA11 24.50 29.50 31.90 34.40 38.70 38.70 38.70 38.70 38.70 MXD10 10.15 12.20 13.20 14.20 16.00 16.00 16.00 16.00 16.00 PPH 5060 11.30 13.50 14.70 15.80 — — — — — CA 100 3.75 4.50 4.90 5.30 — — — — — MH5020 — — — — 10.00 — — — — VA 1803 — — — — — 10.00 — — — VA 1840 — — — — — — 10.00 — — Kraton FG1901 — — — — — — — 10.00 — Fusabond N493 — — — — — — — — 10.00 Antioxidant 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 GF with circular 30 20 20 20 20 20 20 20 20 section (E type) Hollow glass beads 20 20 15 10 15 15 15 15 15 Dk at 1 GHz, 23° C. 2.85 2.81 2.72 2.80 2.81 2.78 2.81 2.81 2.79 and 50% RH Tan delta at 1 GHz, 0.0057 0.0057 0.0059 0.0067 0.0072 0.0071 0.0070 0.0072 0.0071 23° C. and 50% RH Modulus of 9 6.90 7 6 6 6 6 6 6 elasticity E (GPa) I1-I8: Invention 1 to Invention 8 C1: Comparative composition C1 PA11: Rilsan ® (Arkema) PA11/B10 (10:90 by weight) PA11/10T: 1:0.7 molar ratio Polypropylene PPH 5060: ungrafted polypropylene homopolymer from Total Orevac CA 100: maleic anhydride-grafted polypropylene (Arkema) MH5020: Tafmer MH5020 (maleic anhydride-grafted ethylene-butene copolymer marketed by Mitsui Chemicals) VA 1803: EXXELOR ™ VA 1803 (ExxonMobil): Maleic anhydride-grafted ethylene copolymer VA 1840: EXXELOR ™ VA 1840 (ExxonMobil): Maleic anhydride-grafted ethylene copolymer Kraton ™ FG1901 (Kraton): Ethylene and styrene-butene copolymer Fusabond ™ N493 (Dow Chemical): Maleic anhydride-grafted ethylene copolymer E glass fibers: E solid glass fibers with a circular cross-section from Nitto Boseki or Nippon Electric Glass Glass beads: Hollowlite HK60 hollow glass beads Dk, tan delta are measured according to ASTM D-2520-13

[0316] The tensile modulus (or modulus of elasticity E) is measured according to standard ISO 527-1 and 2:2012.

[0317] Several types of hollow beads were tested, whose characteristics are presented in Table 2 and the results are presented in Table 3 according to the same measuring methods as in Table 1.

TABLE-US-00002 TABLE 2 Supplier Hollowlite 3M Grade HK60 HS38 HS70 HL60 iM16K iM30K Characteristics Real density (g/cm3) 0.6 0.4 0.7 0.6 0.5 0.6 of hollow glass Crushing strength 18000 5500 30000 18000 16000 27000 beads (PSI) Particle size 30 30 10 30 20 18 distribution D50 (μm) Presence of enzymes YES NO NO NO NO NO The crushing strength is measured as defined in the 3M safety data sheets (TDS): 3M QCM 14.1.8.

TABLE-US-00003 TABLE 3 I9 I10 I11 I12 I13 I14 PA11 38.70  38.70  38.70  38.70  38.70  38.70  MXD10 — — — — — — PPH 5060 4.50 4.50 4.50 4.50 4.50 4.50 CA 100 1.50 1.50 1.50 1.50 1.50 1.50 MH5020 — — — — — — VA 1803 — — — — — — VA 1840 — — — — — — Kraton FG1901 — — — — — — Fusabond N493 — — — — — — Antioxidant 0.30 0.30 0.30 0.30 0.30 0.30 GF with circular section (E type) 35.00  35.00  35.00  35.00  35.00  35.00  Hollowlite HK60 hollow glass 20.00  — — — — — beads Hollowlite HS38 hollow glass — 20.00  — — — — beads Hollowlite HS70 hollow glass — — 20.00  — — — beads Hollowlite HL60 hollow glass — — — 20.00  — — beads 3M hollow glass beads — — — — 20.00  — iM 16K 3M hollow glass beads — — — — — 20.00  IM 30K Dk at 1 GHz, 23° C. and 50% RH 2.81 3.00 2.90 2.80 2.80 2.80 Tan delta at 1 GHz, 23° C. and  0.0057  0.0060  0.0060  0.0070  0.0070  0.0070 50% RH Modulus of elasticity E (GPa) 6.90 7.20 7.10 7.00 7.10 7.10 I9-I14: Invention 9 to Invention 14