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

Abstract

The use of a mixture of solid and hollow glass reinforcements with an alloy of at least one polyamide and at least one polyolefin, the mixture of solid and hollow glass reinforcements including from 5 to 50% by weight of hollow glass beads relative to the total of solid and hollow glass reinforcements for the dry preparation at 23° C. of a composition having a modulus at least equal to 8 GPa and a dielectric constant Dk less than or equal to 3.5 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 method of using a mixture of solid and hollow glass reinforcements with an alloy consisting of at least one polyamide and at least one polyolefin, said mixture of solid and hollow glass reinforcements comprising from 5 to 50% by weight of hollow glass beads relative to the total of solid and hollow glass reinforcements, excluding polyamide 6 and 66, for the dry preparation, at 23° C., of a composition having a modulus at least equal to 8 GPa, and a dielectric constant Dk, less than or equal to 3.5, as measured according to ASTM D-2520-13, at a frequency of at least 1 GHz, at 23° C., under 50% RH.

2. The method 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 method according to claim 1 or 2, wherein said mixture of solid and hollow glass reinforcements, 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 method according to claim 3, wherein said mixture of glass reinforcements consists of 50 to 95% by weight of solid glass fibers and 5 to 50% by weight of hollow glass beads.

5. The method 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 method 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 method according to claim 6, wherein the reactive units of the grafted polyolefin are chosen from esters of unsaturated carboxylic acids.

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

9. The method 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 method according to claim 6 wherein the ungrafted polyolefin is propylene-based.

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

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

14. The method 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 C6 to C18 amino acid, or of at least one C6 to C18 of at least one C4-C36 aliphatic diamine Ca, with at least one C4-C36 dicarboxylic acid Cb; XY is an aliphatic repeating unit obtained by polycondensation: of at least one cycloaliphatic diamine, or of at least one linear or branched aliphatic diamine X and of at least one aromatic dicarboxylic acid or of at least one aliphatic dicarboxylic acid Y.

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

16. The method 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 method according to claim 16, wherein the semicrystalline polyamide is chosen from aliphatic polyamides.

18. The method according to claim 16, wherein said polyamide mixture is a mixture of an aliphatic polyamide.

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

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

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

22. The method 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 method 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 method according to claim 1, wherein the composition comprises additives.

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

26. A composition comprising: 30 to 70% by weight of an alloy consisting of at least one polyamide and at least one polyolefin, the polyamide/polyolefin ratio being from 95/5 to 50/50; 30 to 70% by weight of a mixture of solid and hollow glass reinforcement; excluding polyamide 6 and 66, and 0 to 11% by weight of at least one prepolymer; 0 to 5% by weight of fillers, and 0 to 2% by weight, the sum of the proportions of each constituent of said composition being equal to 100%.

27. The use of A method of using a composition prepared according to the method of claim 1, for the manufacture of an article.

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

29. An article obtained by injection molding with a composition prepared according to the method of claim 1.

Description

EXAMPLES

[0281] The invention will now be illustrated in greater detail by means of the following examples without being in any way limited to these.

[0282] The various polyamides and copolyamides of the invention were prepared according to the usual techniques for polyamide and copolyamide synthesis.

[0283] 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 chosen 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. When the stoppage conditions are reached, related to the desired viscosity, stirring is stopped and the extrusion and granulation can start.

[0284] 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:

[0285] Twin screw extruder, such as Coperion ZSK 26 MC, with at least 1 lateral raw material inlet

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

Transformation:

[0286] Wafers 100×100×2 mm3 were made by injection moulding for the measurements of the dielectric properties. The following parameters were used: [0287] ENGEL VICTORY 500, 160T hydraulic press [0288] Injection temperature (feed/nozzle): 265C/280C [0289] Mold temperature: 100C [0290] Holding time: 10 s [0291] Material holding pressure: 700 bar [0292] Cooling time: 35 s

[0293] 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: [0294] ENGEL VICTORY 500, 160T hydraulic press [0295] Injection temperature (feed/nozzle): 285C/295C [0296] Mold temperature: 100C [0297] Holding time: 10 s [0298] Material holding pressure: 700 bar [0299] Cooling time: 15 s

[0300] The results obtained from the compositions of the invention are shown in the following Table 1 and Table 2:

TABLE-US-00001 TABLE 1 I1 I2 I3 I4 I5 I6 I7 I8 I9 11/B10 27.72 23.72 PA11 19.6 15.6 19.6 15.6 11.9 11.9 MXD10 8.12 8.12 8.12 8.12 8.12 6.82 6.82 PA11 oligo mono-NH2 4 4 10 4 4 4 PPH 5060 9 9 9 9 9 9 9 9 9 CA 100 3 3 3 3 3 3 3 3 3 Antioxidant 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Secondary antioxidant 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 GF with flat section 40 40 45 (NE type) GF with circular 40 40 40 40 40 45 section (E type) Hollow glass beads 20 20 20 20 20 20 20 20 20 Dk at 1 GHz, 23° C. 3.1 3.0 3.3 3.1 3.1 3.3 3.2 3.4 3.2 and 50% RH Tan delta at 1 GHz, 0.005 0.005 0.006 0.006 0.005 0.006 0.006 0.006 0.005 23° C. and 50% RH Modulus of elasticity E 10.7 11.1 12.0 11.8 12.4 11.5 11.7 14.3 12.9 (GPa)

TABLE-US-00002 TABLE 2 I10 I11 I12 I13 I14 I15 11/B10 8.1 19.6 — — 27.7 — PA11 19.6 — 27.7 — — MXD10 — 8.1 — 8.12 — 11/10T — — — — — 27.7 PA11 oligo mono-NH2 — — — — — — PPH 5060 9 9 9 9 9 9 CA 100 3 3 3 3 3 3 Antioxidant 0.1 0.1 0.1 0.1 0.1 0.1 Secondary antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 GF with flat section — — — — — — (NE type) GF with circular section 40 40 40 40 40 40 (E type) Hollow glass beads 20 20 20 20 20 20 Dk at 1 GHz, 23° C. 2.96 3.03 2.95 3.11 2.99 3.05 and 50% RH Tan delta at 1 GHz, 23° C. 0.007 0.006 0.007 0.004 0.006 0.007 and 50% RH Modulus of elasticity E 11.5 11.4 11.4 13.1 10.5 11.7 (GPa)

[0301] Comparative compositions are shown in the following Table 3:

TABLE-US-00003 TABLE 3 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 PA11 100 55 45 50 11/10T 70 PA10.10 27.62 27.62 27.62 60 60 60 85 70 MXD10 11.84 11.84 11.84 20 PPH 5060 45 55 30 30 Antioxidant 0.08 0.08 0.08 Secondary antioxidant 0.16 0.16 0.16 lubricant 0.3 0.3 0.3 GF with flat section 60 40 (NE type) GF with circular Section 60 40 Nittobo/NEG (E-type) GF with circular section 60 40 S2 (HM type) Hollow glass beads 15 30 Dk at 1 GHz 4.2 3.8 3.9 3.7 4.1 3.9 2.6 2.4 2.8 2.6 2.6 2.7 2.8 Tan delta at 1 GHz 0.009 N/A Modulus of elasticity E 16.0 14.0 16.0 15.0 16.0 17.0 2.0 2.0 1.2 0.9 0.9 1.2 1.4 (GPa) I1 to I9: Invention 1 to 9 C1 to C13: Comparative compositions C1 to C13 N/A: Not tested PA11: Rilsan (Arkema) PA11/10T (28/72 by weight) PA11/B10 (10/90 by weight) Polypropylene PPH 5060: ungrafted polypropylene homopolymer from Total Orevac CA 100: maleic anhydride grafted polypropylene (Arkema) PA oligo: PA11 mono NH2

[0302] Antioxidant refers to an antioxidant of the phenolic type.

[0303] Secondary antioxidant corresponds to an antioxidant of the phosphite type.

NE glass fibers: NE solid glass fibers with a flat cross-section from Nitto Boseki
E glass fibers: E solid glass fibers with a circular cross-section from Nitto Boseki or Nippon Electric Glass
HM glass fibers: solid fibers with a circular cross-section from AGY (high-modulus glass fibers)
Glass beads: Hollowlite glass beads
Dk, tan delta are measured according to ASTM D-2520-13

[0304] The tensile modulus (or modulus of elasticity E) is measured according to ISO 527-1 and 2:2012.