BIO BASED POLYAMIDES AND CORRESPONDING POLYMER COMPOSITIONS
Described herein is a biobased semi-crystalline copolyamide having a combination of thermal properties and being suitable to prepare unfilled and fiber-reinforced thermoplastic compounds and composites prepared from first diamine (DA1) selected in the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD) and a mixture thereof and a second diamine (DA2) selected in the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10) and a mixture thereof.
1 . A polyamide (PA) comprising recurring units (R PA ) formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B) wherein:
the diamine component (A) comprises:
a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD) and a mixture thereof, and
b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10) and a mixture thereof,
wherein the molar ratio DA1/DA2 of the first diamine (DA1) over the second diamine (DA2) is between 5/95 and 47/53; and
wherein the proportion of DA2 in the diamine component (A) is greater than or equal to 53.0 mol % (≥53.0 mol %), this proportion being based on the total amount of diamines in the diamine component (A);
the dicarboxylic acid component (B) comprises:
c) between 70.0 and 95.0 mol. % of terephthalic acid;
d) greater than 5.0 and less than or equal to 30.0 mol. % of another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassilic acid, 1,4-cyclohexanedicarboxylic acid (CHDA) and a mixture thereof,
these proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
2 . The Polyamide (PA) according to claim 1 , wherein the diamine component (A) consists of the first diamine (DA1) and of the second diamine (DA2); or wherein the diamine component (A) consists of the first diamine (DA1), of the second diamine (DA2), and up to 2.0 mol % of at least one diamine other than DA1 and DA2, this proportion in mol % being based on the total amount of diamines in the diamine component (A).
3 . (canceled)
4 . The Polyamide (PA) according to claim 1 , wherein the dicarboxylic acid component (B) or consists of terephthalic acid and the other diacid (DI); or wherein the dicarboxylic acid component (B) consists of terephthalic acid, the other diacid (DI), and up to 2.0 mol % of at least one diacid other than terephthalic acid and other than DI, this proportion in mol % being based on the total amount of diacids in the dicarboxylic acid component (B).
5 . (canceled)
6 . The Polyamide (PA) according to claim 1 , wherein if the diamine component (A) comprises 2-methyl-1,8-octanediamine (MODA), the proportion of MODA in the diamine component (A) is less than or equal to 10.0 mol % (≤10.0 mol %), this proportion in mol % being based on the total amount of diamines in the diamine component (A).
7 . A Polyamide (PA) comprising recurring units (R PA ) formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B) wherein:
the diamine component (A) consists essentially of:
a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD) and a mixture thereof, and
b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10) and a mixture thereof,
wherein the molar ratio DA1/DA2 of the first diamine (DA1) over the second diamine (DA2) is between 5/95 and 47/53;
the dicarboxylic acid component (B) consists essentially of:
c) between 70.0 and 95.0 mol. % of terephthalic acid;
d) greater than 5.0 and less than or equal to 30.0 mol. % of another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassilic acid, 1,4-cyclohexanedicarboxylic acid (CHDA) and a mixture thereof,
these proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
8 . The Polyamide (PA) according to claim 1 , comprising the recurring units (R PA1 ) and (R PA2 ) represented by the following formulae, respectively,
the proportions of these recurring units being as follows:
between 70.0 and 95.0 mol. % of (R PA1 );
greater than 5.0 and less than or equal to 30.0 mol. % of (R PA2 );
where:
R 1 is a divalent radical of a diamine corresponding to the combination of:
a) a first diamine (DA1) is selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD) and a mixture thereof; and
b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10) and a mixture thereof,
the molar ratio DA1/DA2 of the first diamine (DA1) over the second diamine (DA2) being between 5/95 and 47/53;
R 2 is a divalent radical of a diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassilic acid, 1,4-cyclohexanedicarboxylic acid (CHDA) and a mixture thereof;
wherein the total proportion of recurring units RPA1 and RPA2 is at least 95.0 mol % or wherein the recurring units of the polyamide (PA) consist of recurring units RPA1 and RPA2.
9 . (canceled)
10 . (canceled)
11 . (canceled)
12 . (canceled)
13 . The Polyamide (PA) according to claim 1 , wherein the molar ratio DA1/DA2 is:
between 5/95 and 40/60; or
between 15/85 and 47/53; or
between 15/85 and 37/63; or
between 18/82 and 47/53; or
between 8/92 and 37/63; or
between 25/75 and 35/65.
14 . (canceled)
15 . (canceled)
16 . (canceled)
17 . (canceled)
18 . The Polyamide (PA) according to claim 1 , the recurring units (R PA* ) of which are formed from the polycondensation of a diamine component (A) and a diarboxylic acid component (B) wherein:
the diamine component (A) comprises:
a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD) and a mixture thereof, and
b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10) and a mixture thereof,
wherein the proportion of the second diamine (DA2) in the diamine component (A) is between 60.0 and 85.0 mol % and the molar ratio DA1/DA2 of the first diamine (DA1) over the second diamine (DA2) is between 15/85 and 40/60;
the dicarboxylic acid component (B) comprises:
a) between 82.0 and 94.0 mol. % of terephthalic acid;
b) between 6.0 and 18.0 mol. % of isophthalic acid;
these proportions in mol % being based on the total amount of diacids in the dicarboxylic acid component (B); and
exhibiting the following properties:
a melting point Tm of greater than or equal to 240° C. and less than 290° C.;
a glass transition temperature Tg between 115° C. and 135° C.;
Tm and Tg being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, using a heating and cooling rate of 20° C./min;
optionally a bio-content of at least 33.0%, the bio-content being expressed as a % of organic carbon of renewable origin measured according to ASTM D6866-22.
19 . The Polyamide (PA) according to claim 1 , the recurring units of which consist essentially of the recurring units (R PA1 ) and (R PA2 ) with the following proportions relative to the total amount of recurring units in the polyamide (PA):
between 82.0 and 94.0 mol. % of (R PA1 )
between 6.0 and 18.0 mol. % of (R PA2 )
wherein:
R 1 is a divalent radical of a diamine corresponding to the combination of:
a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD) and a mixture thereof; and
b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10) and a mixture thereof,
the molar ratio DA1/DA2 of the first diamine (DA1) over the second diamine (DA2) being between 15/85 and 40/60;
wherein the proportion of the recurring units derived from DA2 is between 60.0 and 85.0 mol %; and
exhibiting the following properties:
a melting point Tm of greater than or equal to 240° C. and less than 290° C.;
a glass transition temperature Tg between 115° C. and 135° C.;
Tm and Tg being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, using a heating and cooling rate of 20° C./min;
optionally a bio-content of at least 33.0%, the bio-content being expressed as a % of organic carbon of renewable origin measured according to ASTM D6866-22.
20 . The Polyamide (PA) according to claim 1 , exhibiting a bio content of at least 30.0%, the bio-content being expressed as a % of organic carbon of renewable origin measured according to ASTM D6866-22.
21 . (canceled)
22 . (canceled)
23 . (canceled)
24 . (canceled)
25 . (canceled)
26 . The Polyamide (PA) according to claim 1 , exhibiting a heat of fusion (Hm) of at least 30.0 J/g, the heat of fusion (Hm) being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, using a heating and cooling rate of 20° C./min; and/or exhibiting the following properties:
a melting point Tm between 240° C. and 300° C.;
a glass transition temperature Tg of at least 115° C.;
Tm and Tg being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, using a heating and cooling rate of 20° C./min;
a bio-content of at least 30.0%, the bio-content being expressed as a % of organic carbon of renewable origin measured according to ASTM D6866-22.
27 . (canceled)
28 . (canceled)
29 . (canceled)
30 . The Polyamide (PA) according to claim 1 , exhibiting a melting point Tm and a glass transition temperature Tg following equation 1 (eq 1):
Tm
/
Tg
<
-
0.0372
×
Tg
(
in
°
C
.
)
+
6.8402
(
eq
.
1
)
Tm and Tg being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, using a heating and cooling rate of 20° C./min.
31 . (canceled)
32 . The Polyamide (PA) according to claim 1 , exhibiting an inherent viscosity (IV) between 0.50 and 1.70 dL/g, the inherent viscosity (IV) being measured according to ASTM D5336-22 with the use of a mixture phenol/trichloroethylene (60/40 wt. ratio).
33 . (canceled)
34 . (canceled)
35 . (canceled)
36 . (canceled)
37 . (canceled)
38 . A process of preparation of a polyamide as defined in claim 1 , consisting of heating a reaction mixture (RM) comprising all the monomers (DA1, DA2, terephtalic acid and DI) in the presence of less than 60 wt. % of water.
39 . A thermoplastic composite (TPC) comprising:
a polymer matrix comprising: (i) the polyamide (PA) according claim 1 , and (ii) optionally at least one plastic additive; and
fibers embedded in the polymer matrix.
40 . (canceled)