SEMI-CRYSTALLINE POLYAMIDE COMPOSITION HAVING A HIGH GLASS TRANSITION TEMPERATURE AND A HIGH MELTING TEMPERATURE FOR A THERMOPLASTIC MATERIAL, PRODUCTION METHOD THEREOF AND USES OF SAME

Abstract

The invention relates to a composition for a thermoplastic material comprising: 0 to 70% by weight, preferably 20 to 60% by weight, of short reinforcing fibers, 30 to 100% by weight, preferably 40 to 80% by weight, of a thermoplastic matrix based on at least one semi-crystalline polyamide polymer, 0 to 50% of additives and/or other polymers,
where said semi-crystalline polyamide polymer is: a) a reactive composition comprising or consisting of at least one reactive polyamide prepolymer precursor of said semi-crystalline polyamide polymer, or in alternative to a), b) a non-reactive composition of at least one polyamide polymer where said composition is that of said thermoplastic matrix defined above,
and said reactive polyamide prepolymer for the composition a) and said polyamide polymer for the composition b) comprising or consisting of at least one BACT/XT copolyamide.

Claims

1. A composition for a thermoplastic material comprising: 0 to 70% by weight of short reinforcing fibers, 30 to 100% by weight of a thermoplastic matrix based on at least one semi-crystalline polyamide polymer, 0 to 50% of additives and/or other polymers, where said composition is: a) a reactive composition comprising at least one reactive polyamide prepolymer precursor of said semi-crystalline polyamide polymer, or in alternative to a), b) a non-reactive composition of at least one polyamide polymer where said composition is that of said thermoplastic matrix defined above, and said reactive polyamide prepolymer for the composition a) and said polyamide polymer for the composition b) comprising at least one BACT/XT copolyamide in which: BACT is a unit with an amide motif present at a molar content ranging from 70 to 99.1% where BAC is selected from the group consisting of 1,3-bis(aminomethypcyclohexyl (1,3-BAC), 1,4-bis(aminomethypcyclohexyl (1,4-BAC) and a mixture thereof, and T is terephthalic acid, XT is a unit with an amide motif present at a molar content ranging from 0.9 to 30% where X is a C.sub.9 to C.sub.18 linear aliphatic diamine, and where T is terephthalic acid, in the BACT and/or XT units, independently of each other, up to 30 mol %, of terephthalic acid, relative to the total quantity of dicarboxylic acids, can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon atoms, and in the BACT and/or XT units, independently of each other, up to 30 mol % of BAC and/or if applicable X, relative to the total quantity of the diamines, can be replaced by other diamines comprising from 4 to 36 carbon atoms, and in the copolyamide, not more than 30 mol % relative to the total quantity of the monomers, can be formed by lactams or aminocarboxylic acids, and provided that the sum of the monomers that replace terephthalic acid, BAC and X does not exceed a concentration of 30 mol %, relative to the total quantity of the monomers used in the copolyamide, and provided that BACT and XT units are still present in said polyamide polymer.

2. The composition according to claim 1, wherein said semi-crystalline polyamide polymer has a melting temperature Tm of from 290 C. to 340 C., as determined according to the ISO 11357-3 (2013) standard.

3. The composition according to claim 1, wherein said semi-crystalline polyamide polymer has a glass transition temperature Tg>150 C., determined according to the ISO 11357-2:2013 standard,

4. The composition according to claim 1, wherein said semi-crystalline polyamide polymer has a difference between the melting temperature and the crystallization temperature TmTc<40 C., determined according to the ISO 11357-3:2013 standard.

5. The composition according to claim 1, that wherein the enthalpy of crystallization of the semi-crystalline polyamide polymer, measured by differential scanning calorimetry (DSC) according to the ISO 11357-3:2013 standard, is greater than 40 J/g.

6. The composition according to claim 1, wherein BAC is 1,3-BAC.

7. The composition according to claim 1, wherein the BAC is 1,3-BAC and XT is chosen from 9T, 10T, 11T and 12T.

8. The composition according to claim 1, wherein the XT is 10T, 10 corresponding to 1,10-decanediamine.

9. The composition according to claim 1, wherein the sum of the monomers that replace terephthalic acid, BAC and X is equal to 0.

10. The composition according to claim 1, wherein said composition is a non-reactive composition according to b).

11. The composition according to claim 1, wherein said polyamide composition is a reactive prepolymer composition according to a) and precursor of said polyamide polymer of said thermoplastic material matrix.

12. The composition according to claim 1, wherein said composition further comprises at least one additive.

13. The composition according to claim 12, wherein the additive is selected from the group consisting of an antioxidant, a thermal stabilizer, a UV absorber, a light stabilizer, an impact modifier, a lubricant, an inorganic filler, a flame retardant agent, a nucleating agent and a colorant.

14. The composition according to claim 1, wherein said composition is a molding composition.

15. A production method for a thermoplastic mechanical part or a structural part made from the composition defined according to claim 1, wherein said method comprises at least one step of polymerization of at least one reactive composition a) or a step of molding or of implementation of at least one non-reactive composition b) by extrusion, injection molding.

16. The method according to claim 15, wherein said method comprises the following steps: injecting into an open or closed mold or without a mold, composition according to claim 1, optionally without fibrous reinforcing, ii) polymerizing in the case of a reactive polyamide composition a) by heating of said composition from step i) with chain extender, by a polycondensation reaction or polyaddition reaction, in bulk in the molten state, with optionally in the case of polycondensation, elimination under vacuum of condensation products when it involves a closed mold, using an extraction system under vacuum, iii) molding of said composition from step i) in the case of a non-reactive polyamide composition b) for forming a final part in a mold and, in the case of a reactive composition a), a step of molding and simultaneously with step ii) of polymerization.

17. A semi-crystalline polyamide polymer, wherein it corresponds to (or is the) polymer from the thermoplastic matrix of said thermoplastic material such as defined according to claim 1, where said polymer is a non-reactive polymer such as defined according to said composition b) or a polymer which could be obtained from a reactive composition such as defined according to said composition a).

18. (canceled)

19. The mechanical or structureal part of claim 23, wherein said mechanical or structural part is a material in a automotive, electrical or electronics, rail, marine, wind power, photovoltaic, solar solar panels and components for solar plants, sports, aeronautics and space, road transport, construction, civil engineering, signs and leisure application.

20. (canceled)

21. (canceled)

22. (canceled)

23. A mechanical or structural part made of said thermoplastic material, of claim 1.

24. The part according to claim 23, wherein said part is a mechanical part in the automobile field selected from the group consisting of parts under the engine hood for the transport of fluid, devices for air intake, devices for cooling of fluids, devices for the cooling of air, transport or transfer of fuel, transport or transfer of oil, and the transport or transfer of water.

25. The part according to claim 23, wherein said part is a mechanical or structural part in the electrical or electronic fields selected from the group consisting of electrical or electronic equipment goods, encapsulated solenoids, pumps, telephones, computers, printers, fax machines, modems, monitors, remote controls, cameras, circuit breakers, electric cable ducts, optical fibers, switches and multimedia systems.

Description

EXAMPLES

[0246] APreparation of a Polyamicie Polymer by Direct Route (without Chain Extension)

[0247] The procedure that follows is an example of a preparation process, and is not limiting. It is representative of all the compositions according to the invention:

[0248] To a 14 liter autoclave reactor, 5 kg of the following raw materials are added: [0249] 500 g water, [0250] the diamines, [0251] the amino acid (optionally), [0252] terephthalic acid and optionally one or the other of the diacids, [0253] the monofunctional chain regulator: benzoic acid in a suitable quantity for the target Mn and varying (benzoic acid) from 50 to 100 g, [0254] 35 g of sodium hypophosphite in solution, [0255] 0.1 g of a WACKER AK1000 antifoam agent (from Wacker Silicones).

[0256] The nature and molar ratios of the molecular motifs and structures of the polyamides (per test, referenced) are given in Table III below.

[0257] The closed reactor is purged of its residual oxygen then heated to a temperature of 230 C. relative to the material added. After 30 minutes of stirring in these conditions, the vapor that formed under pressure in the reactor is relaxed progressively over 60 minutes, while progressively increasing the material temperature so as to establish it at Tm+10 C. at atmospheric pressure.

[0258] The polymerization is then continued under a 20 L/hour nitrogen blanket until a viscous polymer is obtained.

[0259] The polymer is then emptied through the bottom valve then cooled in a water bath then shaped into granules.

[0260] The results are shown in Tables III and IV below. These were obtained starting from 1,3-BAC having a cis/trans ratio of 75/25 mol %.

TABLE-US-00003 TABLE III 10T BACT Tm Tc Tm Tc DeltaHc Tg Ref mol % mol % C. C. C. J/g C. C 100.0 0.0 314 279 35 63 120 10T* I1 16.7 83.3 314.9 291.2 23.7 58.3 176.1 C 0.0 100.0 349 187 BACT* C indicates Comparative I indicates Invention *Per JP2015017177

[0261] The results from Table III show that for a molar fraction of BACT from over 70% to 99.1 mol %, the melting temperature is included from 290 C. to 340 C.

[0262] At the same time, the Tg is very high and can be modulated from 155 C. (not shown in the table) to about 190 C.

TABLE-US-00004 TABLE IV Molecular Tm structure/Molar Tm Tc Tc DeltaHc Tg Inherent Reference Test type composition C. C. C. J/g C. viscosity C1 Comparative 10T/6T (59/41) 281 236 45 44 122 1.12 (EP1,988,113) C2 Comparative 10T/6T/11 (60/24/16) 269 220 49 39 111 1.25 (EP1,988,113) C3 Comparative 10T/TMDT (59/41) 263 197 66 35 133 1.15 (WO2011/00393) C10T Comparative 10T (100) 314 279 35 63 120 insoluble C4 Comparative 10T/11 (67/33) 269 232 37 50 84 1.19 C5 Comparative 10,T/11 (59/41) 261 213 48 39 78 1.15 C6 Comparative 10T/10I (67/33) 269 205 64 32 110 1.12 C7 Comparative MXDT/11 (59/41) 211 (*) >100 12 111 1.25 C8 Comparative MPMDT/11 (59/41) (*) 84 1.14 C9 Comparative 10T/MXDT (50/50) 262 211 51 17 137 0.99 C10 Comparative 10T/MPMDT (59/41) 264 219 45 40 126 1.11 C11 Comparative 10T/MPMDT (50/50) 245 185 60 22 127 1.12 C12 Comparative 10T/12T/11 (60/24/16) 271 246 25 56 105 0.98 C13 Comparative 18T/MXDT (71/29) 264 242 22 47 95 0.86 C14 Comparative 1,3BACT/10T (60/40) 275.6 241.7 33.9 60.8 134.0 0.92 C15 Comparative 1,3BACT/10T (60/40) 281.7 248.3 33.4 53.5 153.4 1.05 C16 Comparative 1,3BACT/10T (45/55) 279.4 242.5 36.9 55.5 146.0 0.93 C17 Comparative 1,3BACT/10T (45/55) 279.8 252.0 27.8 62.2 142.7 0.87 C18 Comparative 1,3BACT/10T (40/60) 282.0 253.5 28.5 49.7 160.2 1.09 C19 Comparative 1,3BACT/10T (40/60) 286.1 250.4 35.7 57.0 163.9 0.94 (*): No crystallization on cooling.

[0263] The results from Table IV show that the total substitution of the BAC or of the 10T motif or a portion of 10T greater than or equal to 30% leads to compositions not having at least one of the required values of Tm, Tg, TmTc and delta Hc.