Copolyamide, composition comprising such a copolyamide and uses thereof

Abstract

The present invention relates to a copolyamide comprising at least two units and corresponding to the following general formula:
A/(diamine).Math.(Cw diacid),
in which: the diamine is a cycloaliphatic diamine, w represents the number of carbon atoms of the diacid, A is chosen from a unit obtained from an amino acid or from a lactam and a unit corresponding to the formula (Cx diamine).Math.(Cy diacid), with x representing the number of carbon atoms of the diamine and y representing the number of carbon atoms of the diacid,
and in which at least one of the monomers chosen from A and the Cw diacid is obtained, in all or part, from renewable starting materials according to Standard ASTM D6866. The invention also relates to a composition comprising this copolyamide and to the use of this copolyamide and of such a composition.

Claims

1. A copolyamide comprising at least two units and having the formula:
A/(diamine).Math.(Cw diacid), in which: the diamine is a cycloaliphatic diamine, w represents the number of carbon atoms of the diacid, and A is a unit obtained from an amino acid that is 9-aminononanoic acid, 10-aminodecanoic acid, 12-aminododecanoic acid, or 11-aminoundecanoic acid, the copolyamide having a molar content of A of up to 64%, and having a glass transition temperature of at least 110° C., and in which at least one of the monomers A and the Cw diacid are obtained, in all or part, from renewable starting materials according to Standard ASTM D6866 in order for the content, expressed as percentage, of renewable organic carbon in the copolyamide, denoted % C.sub.renew.org, of greater than or equal to 54%, the content % C.sub.renew.org corresponding to the following equation (I): $\begin{array}{cc}\%C_{\mathrm{renew}.\mathrm{org}}=\frac{\underset{i}{.Math.}\mathrm{Fi}\times \mathrm{Ci}+\underset{k}{.Math.}\mathrm{Fk}\times {\mathrm{Ck}}^{\prime }}{\left(\underset{j}{.Math.}\mathrm{Fj}\times \mathrm{Cj}+\underset{i}{.Math.}\mathrm{Fi}\times \mathrm{Ci}+\underset{k}{.Math.}\mathrm{Fk}\times \mathrm{Ck}\right)}\times 100& \left(I\right)\end{array}$ with i=monomer(s) resulting from 100% renewable starting materials, within the meaning of Standard ASTM D6866 j=monomer(s) resulting from 100% fossil starting materials, within the meaning of Standard ASTM D6866 k=monomer(s) resulting in part from renewable starting materials, within the meaning of Standard ASTM D6866 Fi, Fj, Fk=respective molar fraction(s) of the monomers i, j and k in the copolyamide Ci, Cj, Ck=respective number of carbon atoms of the monomers i, j and k in the copolyamide, Ck′=number of atoms of renewable organic carbon, within the meaning of Standard ASTM D6866, in the monomer(s) k.

2. The copolyamide according to claim 1, wherein: the molar content of A is between 22 and 64%, and the molar contents of cycloaliphatic diamine and of Cw diacid are each between 18 and 39%.

3. The copolyamide according to claim 1, wherein the cycloaliphatic diamine is bis(3,5-dialkyl-4-aminocyclohexyl)methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4-aminocyclohexyl)propane, bis(3,5-dialkyl-4-amino-cyclohexyl)butane, bis(3-methyl-4-aminocyclohexyl)methane (MACM), p-bis(aminocyclohexyl)-methane (PACM) or isopropylidenedi(cyclohexylamine) (PACP).

4. The copolyamide according to claim 1, wherein the Cw diacid is succinic acid (w=4), adipic acid (w=6), heptanedioic acid (w=7), azelaic acid (w=9), sebacic acid (w=10), undecanedioic acid (w=11), dodecanedioic acid (w=12), brassylic acid (w=13), tetradecanedioic acid (w=14), hexadecanedioic acid (w=16), octadecanedioic acid (w=18), octadecenedioic acid (w=18), eicosanedioic acid (w=20), docosanedioic acid (w=22) or dimer fatty acids having 36 carbons.

5. The copolyamide according to claim 1, of the formula 11/B.10, 11/P.10, 11/B.12, 12/B.12, 11/P.12, 12/P.12, 11/B.14, 11/P.14, 11/B.18 or 11/P.18 wherein B stands for BMAC and P stands for PACM.

6. The copolyamide according to claim 1, additionally comprising at least one third unit such that the copolyamide has the formula:
A/(diamine).Math.(Cw diacid)/(Ct diamine).Math.(Cu diacid) in which t represents the number of carbon atoms of the diamine and u represents the number of carbon atoms of the diacid, wherein at least one of the monomers A, the Cw diacid, the Ct diamine or the Cu diacid is obtained, in all or part, from renewable starting materials according to Standard ASTM D6866, having a content % C.sub.renew.org of greater than or equal to 54%, and wherein the molar content of A is up to 64%, and Ct diamine is a cycloaliphatic diamine.

7. The copolyamide according to claim 6, wherein: the molar content of A is between 22 and 64%, the sum of the molar contents of cycloaliphatic diamine and of Ct diamine, on the one hand, and the sum of the molar contents of Cw and Cu diacids, on the other hand, are each between 18 and 39%.

8. The copolyamide according to claim 6, wherein the Ct diamine is a cycloaliphatic diamine that is bis(3,5-dialkyl-4-aminocyclohexyl)methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4-aminocyclohexyl)propane, bis(3,5-dialkyl-4-aminocyclohexyl)butane, bis(3-methyl-4-aminocyclohexyl)methane (MACM), p-bis(aminocyclohexyl)methane (PACM) or isopropylidenedi(cyclohexylamine) (PACP).

9. The copolyamide according to claim 6, wherein the Cu diacid is succinic acid (u=4), adipic acid (u=6), heptanedioic acid (u=7), azelaic acid (u=9), sebacic acid (u=10), undecanedioic acid (u=11), dodecanedioic acid (u=12), brassylic acid (u=13), tetradecanedioic acid (u=14), hexadecanedioic acid (u=16), octadecanedioic acid (u=18), octadecenedioic acid (u=18), eicosanedioic acid (u=20), docosanedioic acid (u=22) or dimer fatty acids having 36 carbons.

10. The copolyamide according to claim 6, of the formula 11/B.10/P.10, 11/B.12/P.12, 11/B.14/P14, 12/B.10/P.10, 12/B.12/P12, 12/B.14/P.14, 6.10/B.10/P10, 6.10/B.12/P.12, 10.10/B.10/P.10, 10.10/B.12/P.12, 10.12/B.10/P.10, or 10.12/P.12/B.12 wherein B stands for BMAC and P stands for PACM.

11. The copolyamide according to claim 6, wherein t and u are each independently 4-36.

12. A composition comprising at least one copolyamide according to claim 1.

13. The composition according to claim 12, additionally comprising at least one second polymer that is a semicrystalline or amorphous polyamide, a semicrystalline or amorphous copolyamide, a polyetheramide, a polyesteramide or a blend thereof.

14. The composition according to claim 12, wherein the second polymer is obtained, in all or part, from a renewable starting material according to Standard ASTM D6866.

15. The composition according to claim 12, additionally comprising at least one additive of natural and renewable origin according to Standard ASTM D6866, that is fillers, fibres, dyes, stabilizers, plasticizers, impact modifiers, surface-active agents, pigments, brighteners, antioxidants, natural waxes or mixtures thereof.

16. A monolayer structure or a multilayer structure, wherein the monolayer or at least one layer of the multilayer structure comprises a composition according to claim 12.

17. A mono- or multilayer structure according to claim 16, in the form of fibers, of a film, of a pipe, of a hollow body or of an injected component.

18. Lenses, spectacle lenses or spectacle frames, comprising in said lenses or frames a copolymer according to claim 1.

19. The copolyamide according to claim 1, wherein w is 4-36.

20. A copolyamide comprising at least two units and having the formula:
A/(diamine).Math.(Cw diacid), in which: the diamine is a cycloaliphatic diamine, w represents the number of carbon atoms of the diacid, and A is a unit obtained from an amino acid that is 9-aminononanoic acid, 10-aminodecanoic acid, 12-aminododecanoic acid, or 11-aminoundecanoic acid, the copolyamide having a molar content of A of up to 64%, and having a glass transition temperature of 110° C. to 134° C., and in which at least one of the monomers A and the Cw diacid are obtained, in all or part, from renewable starting materials according to Standard ASTM D6866 in order for the content, expressed as percentage, of renewable organic carbon in the copolyamide, denoted % C.sub.renew.org, of greater than or equal to 43%, the content % C.sub.renew.org corresponding to the following equation (I): $\begin{array}{cc}\%C_{\mathrm{renew}.\mathrm{org}}=\frac{\underset{i}{.Math.}\mathrm{Fi}\times \mathrm{Ci}+\underset{k}{.Math.}\mathrm{Fk}\times {\mathrm{Ck}}^{\prime }}{\left(\underset{j}{.Math.}\mathrm{Fj}\times \mathrm{Cj}+\underset{i}{.Math.}\mathrm{Fi}\times \mathrm{Ci}+\underset{k}{.Math.}\mathrm{Fk}\times \mathrm{Ck}\right)}\times 100& \left(I\right)\end{array}$ with i=monomer(s) resulting from 100% renewable starting materials, within the meaning of Standard ASTM D6866 j=monomer(s) resulting from 100% fossil starting materials, within the meaning of Standard ASTM D6866 k=monomer(s) resulting in part from renewable starting materials, within the meaning of Standard ASTM D6866 Fi, Fj, Fk=respective molar fraction(s) of the monomers i, j and k in the copolyamide Ci, Cj, Ck=respective number of carbon atoms of the monomers i, j and k in the copolyamide, Ck′=number of atoms of renewable organic carbon, within the meaning of Standard ASTM D6866, in the monomer(s) k.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 represents a summary of the materials employed in, and results measured in examples.

PREPARATION OF VARIOUS COPOLYAMIDES (TRIALS A TO S)

(2) The monomers used in all or part in trials A to S are as follows: 11-aminoundecanoic acid (denoted A11 in Table 1) supplied by Arkema, CAS 2432-99-7, bis(3-methyl-4-aminocyclohexyl)methane (denoted MACM in Table 1), sold under the name Laromin® C260 by BASF, CAS 6864-37-5, p-bis(aminocyclohexyl)methane (denoted PACM20 in Table 1), comprising 21% by weight of trans/trans isomers, sold under the name Amicure® by Air Products, CAS 1761-71-3, p-bis(aminocyclohexyl)methane (denoted PACM50 in Table 1), comprising 50% by weight of trans/trans isomers, sold by Fluka, CAS 1761-71-3, dodecanedioic acid (denoted DC12 in Table 1), sold by Invista, CAS 693-23-2, sebacic acid (denotes DC10 in Table 1), sold by Sun Chemie, CAS 111-20-6, decanediamine (denoted DA10 in Table 1), sold by Sun Chemie, CAS 646-25-3, hexamethylenediamine or hexanediamine (denoted HDMA in Table 1), sold by Rhodia, CAS 124-09-4, meta-xylylenediamine (denoted MXDA in Table 1), sold by Mitsubishi Gas Chemical, CAS 1477-55-0, lauryllactam, sold by Arkema, CAS 947-04-6.

(3) Various homopolyamides and copolyamides were prepared from 2, 3 or 4 monomers as a mixture with several additives, according to the specific compositions (Examples A to S) given in Table 1.

(4) The preparation process, which can be adapted for all of Examples A to S, will now be described in detail for Example A.

(5) It is specified that the contents by weight of additives indicated below are applicable for all Examples A to S.

(6) The composition of Example A comprises the following monomers and additives (benzoic acid, hypophosphorous acid, Irganox® 1098, which is an antioxidant sold by Ciba, dermineralized water), in the following contents by weight: 7.35 kg of aminoundecanoic acid (36.51 mol) 12.3 kg of decanedioic acid (60.82 mol) 14.58 kg of MACM (61.16 mol) 72.17 g of benzoic acid (0.59 mol) 35 g of Irganox® 1098 8.75 g of hypophosphorous acid (H.sub.3PO.sub.2) 525 g of distilled water

(7) This composition is introduced into a 92 l autoclave reactor which, once closed, is heated with stirring to 260° C. After a phase of maintaining under autogenous pressure for 2 hours, the pressure is then reduced to atmospheric pressure over 1.5 h. The reactor is then degassed for approximately 1 h at 280° C. by flushing with nitrogen.

(8) The homopolyamide or copolyamide obtained is then extruded in the form of laces, cooled in a water bath at ambient temperature and then granulated.

(9) The granules obtained are subsequently dried at 80° C. for 12 h under vacuum, in order to achieve a moisture content of less than 0.1%.

Evaluation of the Homopolyamides and Copolyamides of Examples A to S

(10) The glass transition temperatures (denoted Tg), and also the enthalpies of fusion (in J/g) were measured during the second heating by DSC according to Standard ISO 11357 with heating and cooling rates at 20° C./min.

(11) The measurements obtained have been given in Table 1, thus representing the % C.sub.renew.org content calculated for each of the homopolyamides or copolyamides of Examples A to S.

(12) The copolyamides of Examples A to E and H to S are in accordance with the invention, in the sense that the % C.sub.renew.org content is indeed strictly greater than 0.

(13) In addition, Examples A to C, H to L and O to S are furthermore transparent.

(14) Moreover, it is noted that the glass transition temperatures can vary, in Examples A to E and H to S in accordance with the invention, between 50° C. and 134° C., which allows a person skilled in the art to adjust the formulation of the compositions according to the desired Tg, if the latter criterion is regarded as important.

(15) This comment is very clearly also valid for the compositions according to Examples A to C, H to L and O to S, which are in accordance with the invention and moreover transparent and which have Tg values varying between 60° C. and 134° C.

(16) Generally, Tg values of greater than or equal to 110° C. make it possible to envisage applications, for the items obtained from the copolyamides and compositions according to the invention, for which the thermomechanical strength at high temperatures, for example from 60° C., is advantageous.

Comparison of the Colours Between Formulations of Copolyamides According to the Invention (Examples T to V)

Composition of the Copolyamides of Examples T to V

Example T

(17) 8.05 kg of lauryllactam (40.80 mol) 12.37 kg of decanedioic acid (61.16 mol) 14.58 kg of BMACM (61.16 mol) 72.17 g of benzoic acid (0.59 mol) 35 g of Irganox 1098 3.5 kg of distilled water

Example U

(18) 3.56 kg of decanediamine (20.66 mol) 16.69 kg of decanedioic acid (82.53 mol) 14.75 kg of BMACM (61.88 mol) 72.17 g of benzoic acid (0.59 mol) 35 g of Irganox 1098 525 g of distilled water

Example V

(19) 8.16 kg of aminoundecanoic acid (40.51 mol) 12.32 kg of decanedioic acid (60.92 mol) 14.52 kg of BMACM (60.92 mol) 72.17 g of benzoic acid (0.59 mol) 35 g of Irganox 1098 525 g of distilled water

(20) Examples U and V are manufactured according to the general process described above for Example A, with the preceding compositions U and V.

(21) The process used in the case of Example T is as follows:

(22) A 92 l autoclave reactor is filled with 8.05 kg of lauryllactam (40.80 mol), 12.37 kg of decanedioic acid (61.16 mol), 14.58 kg of BMACM (61.16 mol), 72.17 g of benzoic acid (0.59 mol), 35 g of Irganox 1098 and 3.5 kg of distilled water. The autoclave is then closed and heated with stirring to 280° C. After a phase of maintaining under autogenous pressure for 3 h, the pressure is reduced to atmospheric pressure over 1.5 h and then the reactor is degassed for approximately 1 h at 280° C. by flushing with nitrogen.

(23) The following copolyamides, respectively corresponding to Examples T, U and V according to the invention, are obtained: PA10.10/B.10 (comprising 54% of renewable organic C) PA12/B.10 (30% of renewable organic C) PA11/B.10 (54% of renewable organic C)

(24) The YI (yellow index) was measured according to Standard ASTM E313 on plaques with a thickness of 2 mm. It is represented in the following Table 2.

(25) TABLE-US-00001 TABLE 2 Example Formulation (B.10) mol % YI (ASTM E313) T 12/B.10 75 1.72 U 10.10/B.10   75 1.18 V 11/B.10 75 0.33
Graded from the yellowest to the least yellow, the following are found: 12/B.10>10.10/B.10>11/B.10

CONCLUSION

(26) Of Examples T to V, it is PA11/B.10 which exhibits the lowest yellow index.

(27) Measurement of the Resistance to Stress Cracking in Ethanol:

(28) In order to determine the resistance to stress cracking, injection moulded IFC test specimens are subjected to various strains (up to 2.99%) and immersed according to Standard ISO 22088 in ethanol at ambient temperature for 24 h. The strain shown in the following Table 3 corresponds to that for which breakage of the test specimen occurs. This measurement reflects in particular the ability of the polyamide to withstand surface treatments (cleaning wipes, solvents comprising ethanol).

(29) TABLE-US-00002 TABLE 3 Supplier Formulation Composition % strain Arkema 12/B.I/B.T 30/20/50 molar % 0.50 EMS B.12 50.50 molar % 0.99 Arkema B.14 50.50 molar % 2.99 Arkema 11/B.10 23/77 molar % (Example A) No breaking
Under these strain conditions, it is noticed that PA11/B.10 does not break. The resistance to stress cracking of PA11/B.10 (Example A according to the invention) is better than that of the homopolyamides PAB.14 and PAB.12 (comparative examples) in ethanol.

Measurement of the Refractive Index (n) of These Same Test Specimens

(30) The device used is an Abbe refractometer from Krüss. Bromonaphthalene is used between the prism and the sample in order to make possible good contact between the prism and the test specimen to be studied. B.14.fwdarw.n=1.507 B.12.fwdarw.n=1.510 11/B.10.fwdarw.n=1.511

(31) PA11/B.10 exhibits a refractive index equivalent to that of B.12 and greater than that of PAB.14.

(32) For applications of optical lens and spectacle lens type, the use of PA11/B.10 according to the invention is thus clearly advantageous: in addition to being transparent, PA11/B.10 exhibits a refractive index of 1.511; a very low yellow index and an excellent resistance to stress cracking in ethanol.

(33) With the exception of the cycloaliphatic diamines and the lactams, the amino acids, diamines and diacids mentioned in the present patent application are currently known as being able to result from renewable starting materials within the meaning of Standard ASTM D6866.

(34) Of course, the present patent application is also intended to cover the copolyamides which may be obtained from amino acids, lactams, diamines and/or diacids, in particular cycloaliphatic diamines, for which synthesis routes will be developed in the future starting from renewable (bioresourced) starting materials according to the said Standard ASTM D6866.

(35) Furthermore, copolyamides comprising two or three distinct units have been explicitly described. However, nothing forbids the envisaging of copolyamides comprising more than three distinct units, for example four or five distinct units, each of these multiple units being obtained either from an amino acid or from a lactam or corresponding to the formula (diamine).Math.(diacid), the different units being strictly distinct in pairs and with the proviso that the % C.sub.renew.org content, determined by the equation (I) set out above, is strictly greater than 0.