EP4626949A1 - Bio based transparent polyamides - Google Patents

Bio based transparent polyamides

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Publication number
EP4626949A1
EP4626949A1 EP23837176.9A EP23837176A EP4626949A1 EP 4626949 A1 EP4626949 A1 EP 4626949A1 EP 23837176 A EP23837176 A EP 23837176A EP 4626949 A1 EP4626949 A1 EP 4626949A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
mol
acid
dicarboxylic acid
exhibiting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23837176.9A
Other languages
German (de)
French (fr)
Inventor
Arthur René Henri BERTRAND
Stéphane JEOL
Joel Flores
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syensqo Specialty Polymers USA LLC
Original Assignee
Solvay Specialty Polymers USA LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay Specialty Polymers USA LLC filed Critical Solvay Specialty Polymers USA LLC
Publication of EP4626949A1 publication Critical patent/EP4626949A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids

Definitions

  • Grilamid® TR 90 and Rilsan® Clear G850 Rnew are two examples of transparent polyamide but the glass transition temperature of these two polyamides is lower than 200°C (TR 90: 155°C; G850: 150°C), which is a limitation for some applications.
  • US 5,696,202 discloses a polyamide as the condensation product of dodecanedicarboxylic acid and bis(3-methyl-4-aminocyclohexyl)m ethane) (MACM) exhibiting a Tg of 157°C and a polyamide as the condensation product of decanedioic acid and MACM.
  • US 2010/022742 discloses a transparent, hot-steam-sterilizable copolyamide made of: a) 35-42 mol% of MACM, which may be replaced up to 50% by PACM; b) 35-42 mol% of isophthalic acid, which may be replaced up to 50% by terephthalic acid; and c) 16-30 mol% of laurin lactam.
  • US 2010/022742 also discloses a polyamide with 23 mol% of MACM, 27 mol% of PACM, 34% of isophthalic acid and 16 mol% of dodecanediacid.
  • the polyamide of claim 1 comprises MACM in a proportion higher than 42 mol%.
  • US 2022/0177649 discloses a polyamide with units AB/AC/D wherein: (A) is selected as at least one cycloaliphatic diamine from MACM and PACM; (B) is selected as at least one aromatic dicarboxylic acid from the group consisting of isophthalic acid, naphtalenedicarboxylic acid and terephthalic acid; (C) is selected as at least one aliphatic dicarboxylic acid from the group consisting of decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid and hexadecanedioic acid; (D) is selected as at least one lactam or one aminocarboxylic acid from the group consisting of laurolactame, undecanol actam, 12-aminododecanoic acid and 11
  • EP 4067409 discloses the use of bis-cycloaliphatic monomer with a high renewable carbon index.
  • EP 4067409 discloses in particular a MACM.PACM / 12 polyamide wherein the MACM/PACM molar ratio is in the broad range of 5/95-95/5.
  • the polyamide and the polymer composition of the invention aim at solving this technical problem.
  • the invention relates to a polyamide as disclosed in any one of claims 1-38.
  • the invention also relates to a polymer composition as disclosed in any one of claims 39-46.
  • the proportions of diamines in the diamine component (A) are expressed in mol% and are based on the total amount of diamines in the diamine component (A).
  • the proportions of dicarboxylic acids in the dicarboxylic acid component (B) are expressed in mol% and are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
  • the proportions of recurring units in polyamide (PA) are expressed in mol% and are based on the total amount of recurring units in the polyamide (PA).
  • a dicarboxylic acid is an organic compound containing two carboxyl groups (-COOH).
  • the dicarboxylic acid component (B) comprises: c) between 28.0 and 55.0 mol.% of isophthalic acid; d) between 45.0 and 72.0 mol% of a dicarboxylic acid (DA) selected in the group of nonanedioic acid, decanedioic acid and combinations thereof; these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
  • DA dicarboxylic acid
  • the invention according to this embodiment (El) thus also relates to a polyamide (PA), notably an amorphous polyamide, exhibiting a glass transition temperature (Tg) of at least 170°C and comprising recurring units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein:
  • PA polyamide
  • Tg glass transition temperature
  • the diamine component (A) comprises: a) between 48.0 and 95.0 mol% of MACM; and b) between 5.0 and 52.0 mol% of PACM, these proportions in mol% being based on the total amount of diamines in the diamine component (A);
  • the polyamide (PA) of the invention is formed from the polycondensation of the diamines of the diamine component (A) and the dicarboxylic acids of the dicarboxylic acid component (B).
  • the skilled person understands then that the proportion of -NH2 from the diamine component (A) and the proportion of -COOH from the dicarboxylic acid component (B) are substantially equimolar.
  • the molar ratio -NH2/-COOH can be comprised between 0.9 and 1.1, preferentially between 0.95 and 1.05, even more preferentially between 0.98 and 1.02.
  • the polyamide (PA) disclosed in the present invention thus comprise in reacted form the diamines of the diamine component (A) and the dicarboxylic acids of the dicarboxylic acid component (B) with the proportions indicated herein.
  • the diamine component (A) comprises: a) between 48.0 and 95.0 mol% of MACM; and b) between 5.0 and 52.0 mol% of PACM, these proportions in mol% being based on the total amount of diamines in the diamine component (A).
  • PACM or 4,4'-methylene-bis-cyclohexylamine is the diamine of formula:
  • PACM monomer used for the preparation of polyamide (PA) of the present disclosure is generally in the form of a mixture of three isomers: (trans, trans)- , d'methylene bisfcyclohexylamine], (cA,tra «5)-4,4'-methylene bisfcyclohexylamine] and (cis, cA)-4,4'-methylene bisfcyclohexylamine]. See Macromolecules 1971, Vol. 4, N° 3, 347-350.
  • the PACM monomer used for the preparation of polyamide (PA) of the present disclosure comprises a proportion of (/ra//.s,/ra//.s)-4,4'-methylene bisfcyclohexylamine] between 15.0 and 25.0 mol%, this proportion being relative to the contents of the three isomers.
  • PACM20 disclosed in the experimental section exhibits a proportion of (trans, trans) around 20%.
  • the diamine component (A) preferably does not comprise any lactam.
  • the diamine component (A) preferably does not comprise hexamethylene diamine.
  • the diamine component (A) consists essentially of or consists of MACM and PACM with the proportions indicated herein.
  • the expression “consist essentially” means in the context of the invention in relation to the diamine component that the diamine component (A) comprises MACM and PACM and may also comprise up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of another diamine, this proportion in mol% being based on the total amount of diamines in the diamine component (A).
  • the diamine component (A) consists of MACM, of PACM and up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least one diamine other than MACM and PACM, this proportion in mol% being based on the total amount of diamines in the diamine component (A).
  • the polyamide (PA) generally exhibits a Tg of at most 240°C or at most 220°C.
  • the polyamide (PA) is also characterized by an optimized combination of mechanical and optical properties that make it suitable to prepare transparent objects, notably of the daily life.
  • the polyamide (PA) also usually exhibits a low haze.
  • the haze of the polyamide (PA) measured according to ASTM DI 003 on injection moulded specimens of 3.2 or of 2.5 mm thickness is usually lower than 8.0%, preferably lower than 5.0%, preferably lower than 2.0%.
  • the polyamide (PA) described herein can be prepared by any conventional method adapted to the synthesis of polyamides and polyphthalamides.
  • the polyamide (PA) is generally prepared by polycondensation by heating a reaction mixture (RM) comprising all the monomers ⁇ ie MACM, PACM, isophthalic acid and dicarboxylic acid (DA) selected in the group of azelaic acid, sebacic acid and combinations thereof], preferably in the presence of less than 60 wt.% of water, preferentially less than 30 wt.%, less than 20 wt.%, less than 10 wt.%, preferentially with no added water. This proportion is given based on the total weight of the reaction mixture (RM).
  • the polyamide (PA) is generally produced via the polycondensation in the melt.
  • the reaction mixture (RM) comprises the above-referenced diamines and diacids in a quantity such that the proportion of - COOH groups from the diacids and the proportion of -NH2 groups from the diamines are substantially equimolar.
  • the molar ratio -COOH from the diacids of the dicarboxylic acid component (B) / -NH2 from the diamines from the diamine component (A) can be comprised between 0.9 and 1.1, preferentially between 0.95 and 1.05, even more preferentially between 0.98 and 1.02.
  • the reaction mixture (RM) further preferably comprises a catalyst.
  • the catalyst may be selected in the group consisting of phosphorous acid, ortho-phosphoric acid, metaphosphoric acid, alkali-metal hypophosphite, such as sodium hypophosphite and phenylphosphinic acid, and combination thereof.
  • a convenient catalyst used is sodium hypophosphite.
  • a catalyst notably selected in the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite, such as sodium hypophosphite and phenylphosphinic acid, and combination thereof;
  • reaction mixture optionally water, the proportion of which is less than 60 wt.% of water, preferentially less than 30 wt.%, less than 20 wt.%, less than 10 wt.%, preferentially with no added water, this proportion is given based on the total weight of the reaction mixture (RM).
  • the polycondensation is advantageously performed in a well stirred vessel equipped with means to remove the volatile products of the reaction. As the viscosity of the reaction mixture increases over time, the stirrer is adapted to provide sufficient stirring to the reaction mixture at the beginning of the polymerization and when the conversion of the polycondensation is nearly complete.
  • the polymer composition (C) is prepared by a compounding method comprising a step in which the polymer(s) is/are melted and mixed with the other components of the polymer composition (C).
  • Any equipment generally used for compounding may be used a melt mixer, such as a single screw extruder or a twin screw extruder; a single screw or twin screw kneader or a Banbury mixer.
  • the compounding method may conveniently be performed with an extruder such as a single screw extruder or a twin screw extruder.
  • the components other than the polyphtalamide can be incorporated in the polyphtalamide in a side feeder of the extruder.
  • the polyamide of Exl was prepared with the following recipe: 113.48 g (0.47 mol) of MACM, 10.96 g (0.052 mol) ofPACM20, 52.70 g (0.26 mol) of sebacic acid, 43.28 g of isophthalic acid (0.26 mol), 1.6 g of an aqueous solution of phosphorous acid (5%wt, 0.6 mmol) and 10 g of deionized water were introduced in a stainless-steel autoclave equipped with a mechanical stirrer. The autoclave was purged with nitrogen, then sealed and the temperature in the reactor was gradually increased up to 290°C, while the pressure was regulated to 11 bars.
  • polyamide of example El The transparency of polyamide of example El is preserved after 100 cycles of the steam test. Moreover, only a minor discoloration is observed after 100 cycles. Polyamide of example El also exhibits a higher biobased content than comparative example CE1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Described herein is a polyamide (PA) exhibiting a glass transition temperature (Tg) of at least 170°C and comprising recurring units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B) wherein: - the diamine component (A) comprises: a) between 48.0 and 95.0 mol% of MACM; and b) between 5.0 and 52.0 mol% of PACM, these proportions in mol% being based on the total amount of diamines in the diamine component (A); - the dicarboxylic acid component (B) comprises: c) between 28.0 and 55.0 mol.% of isophthalic acid; d) between 45.0 and 72.0 mol% of a dicarboxylic acid (DA) selected in the group of nonanedioic acid, decanedioic acid and combinations thereof; these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

Description

BIO BASED TRANSPARENT POLYAMIDES
This application claims priority of US patent application No. 63/428,201 filed on 28 November 2022 and European patent application No.
22306986.5 filed on 21 December 2022, the content of which being entirely incorporated herein by reference for all purposes. In case of any incoherency between this application and the two applications that would affect the clarity of a term or expression, it should be made reference to this application only.
[FIELD OF THE INVENTION]
[0001] The invention relates to a steam-resistant biobased transparent polyamide suitable to be used in the preparation of transparent articles.
[BACKGROUND OF THE INVENTION]
[0002] Grilamid® TR 90 and Rilsan® Clear G850 Rnew are two examples of transparent polyamide but the glass transition temperature of these two polyamides is lower than 200°C (TR 90: 155°C; G850: 150°C), which is a limitation for some applications.
[0003] US 2005/272908 discloses transparent a polyamide as the condensation product of: a) at least one diamine selected from the group consisting of aromatic diamines, arylaliphatic diamines, and cycloaliphatic diamines; b) tetradecanedioic acid or of a mixture comprising at least 50 mol % of tetradecanedioic acid and at least one diacid selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and cycloaliphatic dicarboxylic acids.
[0004] US 5,696,202 discloses a polyamide as the condensation product of dodecanedicarboxylic acid and bis(3-methyl-4-aminocyclohexyl)m ethane) (MACM) exhibiting a Tg of 157°C and a polyamide as the condensation product of decanedioic acid and MACM.
[0005] EP 1595907 discloses transparent polyamides based on a cycloaliphatic diamine but with a lower Tg.
[0006] US 2010/022742 (DI) discloses a transparent, hot-steam-sterilizable copolyamide made of: a) 35-42 mol% of MACM, which may be replaced up to 50% by PACM; b) 35-42 mol% of isophthalic acid, which may be replaced up to 50% by terephthalic acid; and c) 16-30 mol% of laurin lactam. US 2010/022742 also discloses a polyamide with 23 mol% of MACM, 27 mol% of PACM, 34% of isophthalic acid and 16 mol% of dodecanediacid. The polyamide of claim 1 comprises MACM in a proportion higher than 42 mol%.
[0007] US 9,453,106 discloses a polyamide prepared with isophthalic and terephthalic acid.
[0008] US 6,277,911 discloses a transparent amorphous polyamide made from at least one alkyl substituted cycloaliphatic diamine having from 14 to 22 carbon atoms selected from the group consisting of 2,6-bis (aminomethyl)-norbornane; 3-aminomethyl-3, 5,5-trimethylcyclohexylamine; bis-(4-aminomethyl cyclohexyl); diaminomethyltricyclodecane; l,3-bis-(aminomethyl)-dicyclohexane; bis-(4-amino-3-methyl-2-2- ethylcyclohexyl)-methane; bis-(4-amino-3,5- diethylcyclohexyl)-methane; 2,2-bis- l,4-bis-(aminomethyl)-di cyclohexane and at least one unbranched aliphatic dicarboxylic acid having 7 to 14 carbon atoms, together with at least one aromatic dicarboxylic acid, which aromatic dicarboxylic acid is present in an amount of not more than 20 mol %. There is no disclosure of the combination of MACM and PACM.
[0009] US 2022/0177649 (D2) discloses a polyamide with units AB/AC/D wherein: (A) is selected as at least one cycloaliphatic diamine from MACM and PACM; (B) is selected as at least one aromatic dicarboxylic acid from the group consisting of isophthalic acid, naphtalenedicarboxylic acid and terephthalic acid; (C) is selected as at least one aliphatic dicarboxylic acid from the group consisting of decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid and hexadecanedioic acid; (D) is selected as at least one lactam or one aminocarboxylic acid from the group consisting of laurolactame, undecanol actam, 12-aminododecanoic acid and 11 -aminoundecaneoic acid.
[0010] EP 4067409 discloses the use of bis-cycloaliphatic monomer with a high renewable carbon index. EP 4067409 discloses in particular a MACM.PACM / 12 polyamide wherein the MACM/PACM molar ratio is in the broad range of 5/95-95/5.
[0011 ] Many articles of our daily life (such as containers) need to be transparent and to exhibit UV resistance. In some applications, there is also a need for steam sterilizable polymer and articles made of this polymer that keep their optical and mechanical properties (e.g. without exhibiting any warpage after exposure to steam) after the sterilization cycles. [0012] In recent years, consumer behaviour has also seen a move towards more sustainable products. This trend is rapidly growing for polymers and the market is requesting polymeric articles with a high biocontent.
[0013] There is therefore a need for a sustainable polymer and a polymer composition comprising said polymer having a high biocontent, which exhibits a combination of mechanical, thermal and optical properties, even after steam sterilization, and which exhibits resistance to UV radiation.
[0014] The polyamide and the polymer composition of the invention aim at solving this technical problem.
IBRIEF DISCLOSURE OF THE INVENTION]
[0015] The invention is set out in the appended set of claims.
[0016] The invention relates to a polyamide as disclosed in any one of claims 1-38.
[0017] The invention also relates to a polymer composition as disclosed in any one of claims 39-46.
[0018] The invention also relates to the use as disclosed in claim 47 and to a container as disclosed in claim 47.
[0019] More precisions and details about these subject-matters are now provided below.
[0020] These definitions apply to the present disclosure.
[0021] wt% means % by weight. Mol% means % by mol.
[0022] Unless otherwise stated, the proportions of recurring units in the polyamide are given in mol% and relative to the total proportion of recurring units in the polyamide.
[0023] When numerical ranges are indicated herein, the end-points of the ranges (even of open-ended ranges such as those comprising "at least” or "at most'”) are included.
[0024] In the present application, unless otherwise indicated, any specific embodiment or technical feature relating to one of the subject-matters of the invention is applicable to and interchangeable with another embodiment or technical feature relating also to said subject matter and disclosed elsewhere in the application.
[0025] The proportions of diamines in the diamine component (A) are expressed in mol% and are based on the total amount of diamines in the diamine component (A). The proportions of dicarboxylic acids in the dicarboxylic acid component (B) are expressed in mol% and are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
[0026] The proportions of recurring units in polyamide (PA) are expressed in mol% and are based on the total amount of recurring units in the polyamide (PA).
[0027] A dicarboxylic acid is an organic compound containing two carboxyl groups (-COOH).
[DETAILED DESCRIPTION OF THE INVENTION]
[0028] The invention relates to a polyamide (PA), notably an amorphous polyamide, exhibiting a glass transition temperature (Tg) of at least 170°C and comprising recurring units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein:
- the diamine component (A) comprises: a) between 48.0 and 95.0 mol% of MACM; and b) between 5.0 and 52.0 mol% of PACM, these proportions in mol% being based on the total amount of diamines in the diamine component (A);
- the dicarboxylic acid component (B) comprises: c) between 28.0 and 55.0 mol.% of isophthalic acid; d) between 45.0 and 72.0 mol% of a dicarboxylic acid (DA) selected in the group of nonanedioic acid, decanedioic acid and combinations thereof; these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
[0029] Embodiment (El): under embodiment (El), the dicarboxylic acid (DA) is decanedioic acid. This embodiment (El) is applicable to any embodiment or details of the present disclosure.
[0030] The invention according to this embodiment (El) thus also relates to a polyamide (PA), notably an amorphous polyamide, exhibiting a glass transition temperature (Tg) of at least 170°C and comprising recurring units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein:
- the diamine component (A) comprises: a) between 48.0 and 95.0 mol% of MACM; and b) between 5.0 and 52.0 mol% of PACM, these proportions in mol% being based on the total amount of diamines in the diamine component (A);
- the dicarboxylic acid component (B) comprises: c) between 28.0 and 55.0 mol.% of isophthalic acid; d) between 45.0 and 72.0 mol% of decanedioic acid; these proportions in mol% being based on the total amount of diacids in the dicarboxylic acid component (B).
[0031] The polyamide (PA) of the invention is formed from the polycondensation of the diamines of the diamine component (A) and the dicarboxylic acids of the dicarboxylic acid component (B). The skilled person understands then that the proportion of -NH2 from the diamine component (A) and the proportion of -COOH from the dicarboxylic acid component (B) are substantially equimolar. Thus, the molar ratio -NH2/-COOH can be comprised between 0.9 and 1.1, preferentially between 0.95 and 1.05, even more preferentially between 0.98 and 1.02.
[0032] The polyamide (PA) disclosed in the present invention thus comprise in reacted form the diamines of the diamine component (A) and the dicarboxylic acids of the dicarboxylic acid component (B) with the proportions indicated herein.
[0033] Details about the diamine component (A) and dicarboxylic acid component (B) are provided below.
[0034] Diamine component (A)
[0035] The diamine component (A) comprises: a) between 48.0 and 95.0 mol% of MACM; and b) between 5.0 and 52.0 mol% of PACM, these proportions in mol% being based on the total amount of diamines in the diamine component (A).
[0036] The combination of MACM and PACM in the proportions given herein makes it possible to have a polyamide meeting the aforementioned requirements.
[0037] MACM or 4,4’-methylene-bis(2-methylcyclohexylamine) is the diamine of formula:
PACM or 4,4'-methylene-bis-cyclohexylamine is the diamine of formula:
[0038] The PACM monomer used for the preparation of polyamide (PA) of the present disclosure is generally in the form of a mixture of three isomers: (trans, trans)- , d'methylene bisfcyclohexylamine], (cA,tra«5)-4,4'-methylene bisfcyclohexylamine] and (cis, cA)-4,4'-methylene bisfcyclohexylamine]. See Macromolecules 1971, Vol. 4, N° 3, 347-350. Preferably, the PACM monomer used for the preparation of polyamide (PA) of the present disclosure comprises a proportion of (/ra//.s,/ra//.s)-4,4'-methylene bisfcyclohexylamine] between 15.0 and 25.0 mol%, this proportion being relative to the contents of the three isomers. As an example, PACM20 disclosed in the experimental section exhibits a proportion of (trans, trans) around 20%.
[0039] The diamine component (A) preferably does not comprise any lactam. The diamine component (A) preferably does not comprise hexamethylene diamine.
[0040] According to an embodiment, the diamine component (A) consists essentially of or consists of MACM and PACM with the proportions indicated herein. The expression "consist essentially" means in the context of the invention in relation to the diamine component that the diamine component (A) comprises MACM and PACM and may also comprise up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of another diamine, this proportion in mol% being based on the total amount of diamines in the diamine component (A). In other words, the diamine component (A) consists of MACM, of PACM and up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least one diamine other than MACM and PACM, this proportion in mol% being based on the total amount of diamines in the diamine component (A).
[0041] Dicarboxylic acid component (B)
[0042] The dicarboxylic acid component (B) comprises:
- between 28.0 and 55.0 mol.% of isophthalic acid;
- between 45.0 and 72.0 mol% of a dicarboxylic acid (DA) selected in the group of nonanedioic acid, decanedioic acid and combinations thereof; these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B). [0043] According to an embodiment, the dicarboxylic acid (DA) is nonanedioic acid.
[0044] According to another embodiment (El), the dicarboxylic acid (DA) is decanedioic acid (or sebacic acid). According to this embodiment, the dicarboxylic acid component (B) comprises:
- between 28.0 and 55.0 mol.% of isophthalic acid;
- between 45.0 and 72.0 mol% of decanedioic acid; these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
[0045] Nonanedioic acid (or azelaic acid) is the diacid of formula: HOOC-(CH2)?-COOH. [0046] Decanedioic acid (or sebacic acid) is the diacid of formula: HOOC-(CH2)s-COOH. [0047] The dicarboxylic acid component (B) preferably does not comprise terephthalic acid.
The dicarboxylic acid component (B) preferably does not comprise dodecanedioic acid (HOOC-(CH2)IO-COOH).
[0048] According to an embodiment, the dicarboxylic acid component (B) consists essentially of or consists of isophthalic acid and dicarboxylic acid (DA). The expression "consist essentially" means in the context of the invention in relation to the dicarboxylic acid component (B) that the dicarboxylic acid component (B) consists of isophthalic acid, of dicarboxylic acid (DA) and up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least one dicarboxylic acid other than isophthalic acid and dicarboxylic acid (DA), this proportion in mol% being based on the total amount of the dicarboxylic acids in the dicarboxylic acid component (B).
[0049] According to this embodiment and embodiment (El), the dicarboxylic acid component (B) consists of isophthalic acid, of decanedioic acid and up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least one diacid other than isophthalic acid and decanedioic acid, this proportion in mol% being based on the total amount of the dicarboxylic acids in the dicarboxylic acid component (B).
[0050] The content of aromatic in the polyamide (PA) is usually lower than 11.0 wt%, preferably lower than 10.0 wt%. The aromatic content corresponds to the weight of the carbon and hydrogen atoms of the aromatic rings that are present in the macromolecules of polyamide (PA) relative to the total weight of macromolecules of polyamide (PA). Thus, in the case of a polyamide (PA) based on a diamine component (A) consisting of MACM and PACM and on a dicarboxylic acid component (B) consisting of isophthalic acid and sebacic acid, the carbon and hydrogen atoms to be considered are only those stemming from isophthalic acid. For clarity, as the aromatic content is based on the macromolecules of polyamide (PA) only, one does not take into account the presence of other components such as additives that may be present in the polyamide (PA). A low aromatic content is beneficial for the UV resistance of the polyamide (PA).
[0051] Embodiment (E2): according to a preferred embodiment (E2), the polyamide (PA) comprises recurring units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B) wherein:
- the diamine component (A) comprises, consists essentially of or consists of a) between 85.0 and 95.0 mol% of MACM; and b) between 5.0 and 15.0 mol% of PACM, these proportions in mol% being based on the total amount of diamines in the diamine component (A);
- the dicarboxylic acid component (B) comprises, consists essentially of or consists of c) between 45.0 and 55.0 mol.% of isophthalic acid; d) between 45.0 and 55.0 mol% of dicarboxylic acid (DA) selected in the group of nonanedioic acid, decanedioic acid and combinations thereof; these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
[0052] The proportion of MACM may more particularly be between 87.0 and 93.0 mol% or between 88.0 and 92.0 mol% or between 89.0 and 91.0 mol%; and/or the proportion of PACM may more particularly be between 7.0 and 13.0 mol% or between 8.0 and 12.0 mol% or between 9.0 and 11.0 mol%.
[0053] The proportion of isophthalic acid may be between 47.0 and 53.0 mol% or between 48.0 and 52.0 mol% or between 49.0 and 51.0 mol%; and/or the proportion of dicarboxylic acid (DA) may be between 47.0 and 53.0 mol% or between 48.0 and 52.0 mol% or between 49.0 and 51.0 mol%.
[0054] Embodiment (El) applies to embodiment (E2).
[0055] Embodiment (E3): according to another preferred embodiment (E3), the polyamide (PA) comprises recurring units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B) wherein:
- the diamine component (A) comprises, consists essentially of or consists of: a) between 88.0 and 92.0 mol% of MACM; and b) between 8.0 and 12.0 mol% of PACM, these proportions in mol% being based on the total amount of diamines in the diamine component (A);
- the dicarboxylic acid component (B) comprises, consists essentially of or consists of c) between 48.0 and 52.0 mol.% of isophthalic acid; d) between 48.0 and 52.0 mol% of dicarboxylic acid (DA) selected in the group of nonanedioic acid, decanedioic acid and combinations thereof; these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).
[0056] Embodiment (El) applies to embodiment (E3).
[0057] Recurring units in the polyamide (PA)
[0058] The invention also relates to a polyamide (PA) as defined in claim 12.
[0059] The skilled person understands that the polycondensation of the above-defined monomers lead to a polyamide (PA) comprising the recurring units (RPAI) and (RPA2) where (RPAI) is represented by the formula (I): and/or (lib), where the substituents Xi and X2 on the cyclohexane rings are either both Me or both H and where the proportions of these substituents Me and H in the polyamide (PA) are the following: between 48.0 and 95.0 mol% of Me; and between 5.0 and 52.0 mol% of H.
[0060] Likewise, according to embodiment (El), the skilled person understands that the polycondensation of the above-defined monomers lead to a polyamide (PA) comprising the recurring units (RPAI) and (RPA2) which are represented by the following formulae, respectively, where the substituents Xi and X2 on the cyclohexane rings are either both Me or both H and where the proportions of these substituents Me and H in the polyamide (PA) are the following: between 48.0 and 95.0 mol% of Me; and between 5.0 and 52.0 mol% of H.
[0061] These two units (RPAI) and (RPA2) include carbonyl -(C=O)- and -NH- groups and the polyamide (PA) is a polymer with units linked by amide bonds.
[0062] (RPAI) is derived from isophthalic acid and (RPA2) is derived from nonanedioic acid and/or decanedioic acid.
[0063] The proportions given herein for MACM and for PACM apply for the proportions respectively of substituents Me and substituents H. The proportions of the substituents can be measured by TH NMR.
[0064] The polyamide (PA) disclosed in the present disclosure preferably does not comprise any recurring unit derived from a lactam. The polyamide (PA) disclosed in the present disclosure preferably does not comprise any recurring unit derived from hexamethylenediamine. The polyamide (PA) disclosed in the present disclosure preferably does not comprise any recurring unit derived from terephthalic acid or dodecanedioic diacid. The polyamide (PA) disclosed in the present disclosure preferably does not comprise any recurring unit derived from an aminoacid.
[0065] According to a preferred embodiment, the recurring units of polyamide (PA) of the present disclosure consist essentially in or consist in recurring units (RPAI) and (RPA2).
[0066] The expression "consist essentially" in relation to the recurring units means that the recurring units of polyamide (PA) consist of recurring units (RPAI), (RPA2) and up to 2.0 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol% of recurring units other than (RPAI) and (RPA2).
[0067] Proportion of recurring units (RPAI) and
[0068] The proportion of recurring units (RPAI) is between 28.0 and 55.0 mol%.
[0069] The proportion of recurring units (RPA2) is between 45.0 and 72.0 mol%.
[0070] These proportions are given relative to the total amount of recurring units in the polyamide (PA).
[0071] All the proportions given herein for isophthalic acid, notably in embodiment (E3), apply equally for the proportion of recurring units (RPAI). Likewise, all the proportions given herein for dicarboxylic acid (DA), notably in embodiment (E3), apply equally for the proportion of recurring units (RPA2).
[0072] The invention also preferably relates to a polyamide (PA) comprising the recurring units (RPAI) and (RPAI), notably according to embodiment (El), and defined by the following proportions:
- between 85.0 and 95.0 mol% of Me;
- between 5.0 and 15.0 mol% of H;
- recurring units (RPAI): between 45.0 and 55.0 mol%;
- recurring units (RPA2): between 45.0 and 55.0 mol%. or by the following proportions:
- between 88.0 and 92.0 mol% of Me;
- between 8.0 and 12.0 mol% of H;
- recurring units (RPAI): between 48.0 and 52.0 mol%;
- recurring units (RPA2): between 48.0 and 52.0 mol%.
[0073] The polyamide (PA) of the invention generally has a number average molecular weight ("Mn") of at least 10,000 g/mol. Mn may be at least 12, 000 g/mol, most preferably at least 14,000 g/mol. Mn is generally at most 20,000 g/mol or at most 15,000 g/mol. Mn can be determined using the following equation (1): Mn = 2,000,000 / [EG] (1) wherein [EG] is the proportion of end-groups in the PA expressed in mmol/kg. More precisely, known methods exist to measure the proportion of the amine end-groups and acid end groups.
[0074] The end-groups in the polyamide (PA) are selected in the group of -NEE, -COOH and amide end-groups. Indeed, the end-groups in the polyamide (PA) may be -NEE or - COOH. Yet, when the polycondensation involves the addition of an end-capping agent selected in the group of monocarboxylic acids, primary amines and combination thereof, these end-groups may be converted, partially or totally, into amide end- groups.
[0075] The amide end groups are of formula -NH-C(=0)-R where R is an an alkyl group, an aryl group or a cycloalkyl group and/or of formula -C(=O)-NH-R' where R' is an alkyl group or a cycloalkyl group. R is more particularly a linear or branched Ci-Cis alkyl group or a C5-C10 cycloalkyl group. R' is more particularly a linear or branched C2- Ci8 alkyl group.
[0076] The amide end groups of formula -NH-C(=O)-R result from the reaction of the end- groups -NH2 with a monocarboxylic acid (end-capping agent) of formula R-COOH.
[0077] The monocarboxylic acid (end-capping agent) may advantageously be selected in the group consisting of benzoic acid; cyclohexanoic acid; R-COOH where R is a linear or branched Ci-Cis alkyl group and combination of two or more of these acids. R is the radical derived from the acid of formula R-COOH.
[0078] The monocarboxylic acid (end-capping agent) may more particularly be selected in the group consisting of acetic acid, propanoic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid and combination of two or more of these acids.
[0079] The monocarboxylic acid (end-capping agent) is more particularly of formula CH3- (CH2)n-COOH where n is an integer between 0 and 17. The amide end groups are then of formula -NH-C(=O)-(CH2)n-CH3.
[0080] The amide end groups of formula -C(=O)-NH-R' result from the reaction of the end- groups -COOH with a primary amine (end-capping agent) of formula -NH2.
[0081] The primary amine (end-capping agent) may advantageously be selected in the group consisting of the amines of formula R-NH2 where R' is a linear or branched C2-C18 alkyl group. R' is the radical derived from the amine of formula R-NH2.
[0082] The primary amine (end-capping agent) is more particularly of formula CH3-(CH2)n- NH2 where n' is an integer between 1 and 17. The amide end groups are then of formula -C(=O)-NH-(CH2)n-CH3.
[0083] The primary amine (end capping agent) may more particularly be selected in the group consisting of propyl amine, butylamine, pentylamine, hexylamine, 2- ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n- hexadecylamine, stearylamine, cyclohexylamine and combination of two or more of these amines. [0084] The proportion of the end groups can be quantified by NMR or by potentiomtric techniques.
[0085] Bio content of polyamide (PA)
[0086] The polyamide (PA) may preferably exhibit a bio content of at least 20.0%. The biocontent is expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.
[0087] Nonanedioic acid (azelaic acid) and decanedioic acid (sebacid acid) may be derived from petroleum or natural gas. They may also be biobased as defined in ASTM D6866-22. A product is defined as "biobased" if it contains organic carbon of renewable origin like agricultural, plant, animal, fungi, microorganisms, marine, or forestry materials living in a natural environment in equilibrium with the atmosphere.
[0088] The use of biobased nonanedioic acid (azelaic acid may be prepared from oleic acid: see "Azelaic acid: a bio-based building block for biodegradable polymers" Polymers (Basel). 2021 Nov 24;13(23):4091; DOI 10.3390/polyml3234091) and/or biobased decanedioic acid (sebacic acid may be prepared from castor oil) makes it possible to obtain this level of bio content.
[0089] The bio content is defined as the % of organic carbon of renewable origin. It corresponds to the amount of C calculated from measured 14C percent in the sample and corrected for isotopic fraction.
[0090] According to an embodiment, biobased isophthalic may be used in the preparation of the polyamide (PA). A method of preparation of a biobased isophthalic acid is for instance disclosed in WO 2014/144843. With the use of a biobased isophthalic acid, the bio content of polyamide (PA) may be at least 35.0%.
[0091] According to an embodiment, biobased MACM and PACM may be used in the preparation of the polyamide (PA). These diamines may be prepared from biobased toluene and aniline by hydrogenation of the corresponding aromatic diamines according to EP 0618188. See also EP 4067409. With the use of a biobased MACM and PACM, the bio content of the polyamide (PA) may be at least 80.0%.
[0092] The biocontent of polyamide (PA) may also be at least 90.0% and it can reach 100%.
[0093] The biocontent of polyamide (PA) may be between 20.0 and 100% or between 35.0 and 100% or between 80.0 and 100%.
[0094] According to an embodiment, the polyamide (PA) disclosed herein is prepared from biobased azelaic acid and/or sebacic acid exhibiting a bio content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866- 22.
[0095] According to another embodiment, the polyamide (PA) disclosed herein is prepared from MACM and/or PACM exhibiting a bio content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.
[0096] According to another embodiment, the polyamide (PA) disclosed herein is prepared from isophthalic acid exhibiting a bio content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.
[0097] Moisture absorption of polyamide (PA)
[0098] The polyamide (PA) advantageously exhibits a water uptake at 23°C lower than 5.0 wt%. This water uptake may be less than 3.5 wt%.
[0099] The water uptake at 23°C is determined by (i) providing a specimen shaped according to ISO527 in its dry state (moisture content of less than 0.2 wt.%), (ii) immersing the same in deionized water at 23°C, until reaching a constant weight, (iii) calculating the water uptake with the formula:
W „ - Wh f
Water uptake - - ^-x1 00
Wbefore wherein Wbefore is the weight of the shaped specimen in its original dry state and Waiter is the weight of the shaped specimen after water uptake.
[00100] Thermal and mechanical properties of the polyamide (PA) of the present disclosure
[00101] As noted above, it was surprisingly found that the polyamide (PA) of the invention exhibits a combination of thermal properties.
[00102] 1) Heat of fusion (Hm)
[00103] The polyamide (PA) is amorphous.
[00104] The polyamide (PA) usually exhibits a heat of fusion (Hm) of at most 5.0 J/g, preferably at most 2.0 J/g.
[00105] Hm can be measured by Differential Scanning Calorimetry (“DSC”) according to ISO 11357, using a heating and cooling rate of 20°C/min.
[00106] Hm can more particularly be measured as described in the experimental section. [00107] Hm can be measured by Differential Scanning Calorimetry (“DSC”) according to ISO 11357 using a heating and cooling rate of 20°C/min. Three scans are used for each DSC test: a first heat up to 320°C, followed by a first cool down to -40°C, followed by a second heat up to 320°C.
[00108] 2) Glass transition temperature
[00109] The polyamide (PA) exhibits a Tg of at least 170°C. The Tg of polyamide (PA) may preferably be at least 190°C.
[00110] The Tg of the polyamide (PA), notably for embodiment (E2) or (E3), is preferably at least 200°C, preferably at least 201 °C.
[00111] The Tg of the polyamide (PA), notably for embodiment (E2) or (E3), is preferably greater than or equal to 200.0°C, preferably greater than or equal to 201.0°C.
[00112] The polyamide (PA) generally exhibits a Tg of at most 240°C or at most 220°C.
[00113] Tg may thus be between 200 and 240°C or between 201 and 240°C.
[00114] The glass transition temperature Tg defined in this invention is conveniently measured by Differential Scanning Calorimetry (“DSC”) according to ISO 11357, notably using a heating and cooling rate of 20°C/min.
[00115] Tg can more particularly be measured as described in the experimental section.
[00116] Tg can be measured by Differential Scanning Calorimetry (“DSC”) according to ISO 11357 using a heating and cooling rate of 20°C/min. Three scans are used for each DSC test: a first heat up to 320°C, followed by a first cool down to -40°C, followed by a second heat up to 320°C. The Tg is determined from the second heat up.
[00117] Mechanical and optical properties of polyamide (PA) of the present diclosure
[00118] The polyamide (PA) is also characterized by an optimized combination of mechanical and optical properties that make it suitable to prepare transparent objects, notably of the daily life.
[00119] The polyamide (PA) may exhibit at least one of the following mechanical properties: a tensile modulus measured according to ASTM D638 of at least 2.0 GPa; and/or a tensile strength measured according to ASTM D638 of at least 80.0 MPa; and/or an elongation at break measured according to ASTM D638 of at least 12.0%; and/or an izod impact energy measured according to ASTM D256 of at least 65.0 J/m. [00120] The polyamide (PA) usually also exhibits a transparency of at least 90.0%, preferably at least 95.0% when measured according to ASTM DI 003 on an injection moulded specimen of 3.2 or of 2.5 mm thickness.
[00121] Furthermore, the polyamide (PA) also usually exhibits a low haze. The haze of the polyamide (PA) measured according to ASTM DI 003 on injection moulded specimens of 3.2 or of 2.5 mm thickness is usually lower than 8.0%, preferably lower than 5.0%, preferably lower than 2.0%.
[00122] Process of preparation of the polyamide (PA)
[00123] The polyamide (PA) described herein can be prepared by any conventional method adapted to the synthesis of polyamides and polyphthalamides.
[00124] The polyamide (PA) is generally prepared by polycondensation by heating a reaction mixture (RM) comprising all the monomers \ie MACM, PACM, isophthalic acid and dicarboxylic acid (DA) selected in the group of azelaic acid, sebacic acid and combinations thereof], preferably in the presence of less than 60 wt.% of water, preferentially less than 30 wt.%, less than 20 wt.%, less than 10 wt.%, preferentially with no added water. This proportion is given based on the total weight of the reaction mixture (RM). The polyamide (PA) is generally produced via the polycondensation in the melt.
[00125] As is well known in polycondensation, the reaction mixture (RM) comprises the above-referenced diamines and diacids in a quantity such that the proportion of - COOH groups from the diacids and the proportion of -NH2 groups from the diamines are substantially equimolar. The molar ratio -COOH from the diacids of the dicarboxylic acid component (B) / -NH2 from the diamines from the diamine component (A) can be comprised between 0.9 and 1.1, preferentially between 0.95 and 1.05, even more preferentially between 0.98 and 1.02.
[00126] The reaction mixture (RM) further preferably comprises a catalyst. The catalyst may be selected in the group consisting of phosphorous acid, ortho-phosphoric acid, metaphosphoric acid, alkali-metal hypophosphite, such as sodium hypophosphite and phenylphosphinic acid, and combination thereof. A convenient catalyst used is sodium hypophosphite.
[00127] The reaction mixture (RM) may also further comprise at least one end-capping agent as disclosed above. The end-capping agent may notably be used to control the molecular weight. [00128] According to an embodiment of the present disclosure, the reaction mixture (RM) consists of:
- MACM, PACM, isophthalic acid and dicarboxylic acid (DA) selected in the group of azelaic acid, sebacic acid and combinations thereof; preferably the dicarboxylic acid (DA) is sebacic acid;
- optionally a catalyst, notably selected in the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite, such as sodium hypophosphite and phenylphosphinic acid, and combination thereof;
- optionally at least one end-capping agent selected in the group of monocarboxylic acids, primary amines and combination thereof;
- optionally water, the proportion of which is less than 60 wt.% of water, preferentially less than 30 wt.%, less than 20 wt.%, less than 10 wt.%, preferentially with no added water, this proportion is given based on the total weight of the reaction mixture (RM).
[00129] The temperature at which the reaction mixture is heated must be high enough to induce the reaction between the amine groups and the carboxylic groups of the monomers and to decrease the viscosity of the mixture. This temperature is generally at least 200°C. This temperature is preferably > Tg + 80°C. The polycondensation results in the formation of the amide bonds and the release of water as a by-product.
[00130] The temperature can be step-wise increased in the course of the polycondensation. An example of step-wise increase is given for example 1.
[00131] The polycondensation is advantageously performed in a well stirred vessel equipped with means to remove the volatile products of the reaction. As the viscosity of the reaction mixture increases over time, the stirrer is adapted to provide sufficient stirring to the reaction mixture at the beginning of the polymerization and when the conversion of the polycondensation is nearly complete.
[00132] The conditions disclosed in the experimental section may conveniently be used for the preparation of the polyamide (PA).
[00133] Polymer composition (C)
[00134] The invention also relates to a polymer composition (C) comprising: at least one polyamide (PA) as disclosed herein; at least one polymer additive selected in the group consisting of heat stabilizers, UV stabilizers, colorants, antistatic agents and combination of two or more of said additives. [00135] More particularly, the polymer composition (C) comprises at least one colorant and/or at least one UV stabilizer.
[00136] The polymer(s) and the polymer additive(s) of the polymer composition (C) are preferably blended.
[00137] The proportion of the polymer additive(s) in the polymer composition (C) may be between 0 and 10.0 wt%, this proportion being based on the total weight of the polymer composition (C). This proportion is generally between 0.5 and 10.0 wt%.
[00138] The polymer composition (C) may also comprise a polyamide different from and blended with the polyamide (PA).
[00139] The polymer composition (C) preferably exhibits the mechanical properties as mentioned above. Likewise, the polymer composition (C) preferably exhibits the optical properties as mentioned above.
[00140] The polymer composition (C) is prepared by a compounding method comprising a step in which the polymer(s) is/are melted and mixed with the other components of the polymer composition (C). Any equipment generally used for compounding may be used a melt mixer, such as a single screw extruder or a twin screw extruder; a single screw or twin screw kneader or a Banbury mixer. The compounding method may conveniently be performed with an extruder such as a single screw extruder or a twin screw extruder. The components other than the polyphtalamide can be incorporated in the polyphtalamide in a side feeder of the extruder.
[00141] Use of the polyamide (PA) or of the polymer composition (C)
[00142] The polyamide (PA) and the polymer composition (C) may be used for the preparation of articles, notably transparent articles, and notably transparent articles of the daily life.
[00143] These articles can be prepared from polyamide (PA) or polymer composition (C) by injection moulding
[00144] The polyamide (PA) and the polymer composition (C) may be used for the preparation of decorative articles (in particular in the automobile interior); sport articles (in particular ski boots, midsoles for sport shoes); toys; household articles (in particular containers, dishes, bowls, tins, beakers, baby bottles, drinking bottles, components of kitchen appliances); components of spectacles (in particular spectacle frames or spectacle sidepieces, safety goggles); medical objects (in particular containers, syringes); parts of smart phones (in particular protective covers). [00145] The polyamide (PA) and the polymer composition (C) may be used for the preparation of a container, notably a transparent container. The invention also relates to a container notably a transparent container, made of the polymer composition (C) as disclosed herein.
[EXPERIMENTAL SECTION]
[00146] The present examples demonstrate the synthesis, thermal performance, and mechanical performance and resistance to sterilization of the polyamide of the invention.
[00147] Raw materials used for the preparation of the polyamide (PA) according to the invention
[00148] The following monomers were used:
[00149] Thermal properties
[00150] Thermal properties were measured by Differential Scanning Calorimetry (“DSC”) according to ISO 11357 using a heating and cooling rate of 20°C/min. Three scans are used for each DSC test: a first heat up to 320°C, followed by a first cool down to - 40°C, followed by a second heat up to 320°C. The Tg is determined from the second heat up.
[00151] Steam sterilization test
[00152] The steam-sterilization test consists in submitting a sample of polyamide to 100 cycles of exposure to overheated water vapor (134°C, 3 bars abs., 18 min per cycle). Transparency and warpage are evaluated qualitatively after testing.
[00153] Preparation of the polyamides (PA) of table I
[00154] All of the copolyamides disclosed in Table I were prepared in an autoclave reactor equipped with a distillate line fitted with a pressure control valve. The procedure detailed below for El was followed for the preparation of all copolyamides.
[00155] Example 1 (El)
[00156] The polyamide of Exl was prepared with the following recipe: 113.48 g (0.47 mol) of MACM, 10.96 g (0.052 mol) ofPACM20, 52.70 g (0.26 mol) of sebacic acid, 43.28 g of isophthalic acid (0.26 mol), 1.6 g of an aqueous solution of phosphorous acid (5%wt, 0.6 mmol) and 10 g of deionized water were introduced in a stainless-steel autoclave equipped with a mechanical stirrer. The autoclave was purged with nitrogen, then sealed and the temperature in the reactor was gradually increased up to 290°C, while the pressure was regulated to 11 bars. Upon reaching 290°C, the pressure was gradually reduced to 1 bar while the temperature was further increased up to 310°C. The pressure was then further reduced down to about 130 mbar and the reaction mixture was kept 15 min at 310°C/130 mbars. The pressure was returned to 1 bar through nitrogen gas and the polymer was discharged as a strand and pelletized.
Table I
1 : contents of the diamine component (A) and dicarboxylic acid component (B) are given in mol% ***: transparency fully preserved, no warpage; **: some haze, no warpage; *: near-opaque, warpage % aromatic: is given in wt% and corresponds to the weight of C and H from the aromatic rings that form part of the macromolecules of polyamide (PA) relative to the total weight
[00157] The transparency of polyamide of example El is preserved after 100 cycles of the steam test. Moreover, only a minor discoloration is observed after 100 cycles. Polyamide of example El also exhibits a higher biobased content than comparative example CE1.

Claims

Claim 1. Polyamide (PA) exhibiting a glass transition temperature (Tg) of at least 170°C and comprising recurring units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B) wherein:
- the diamine component (A) comprises: these proportions in mol% being based on the total amount of diamines in the diamine component (A);
- the dicarboxylic acid component (B) comprises: c) between 28.0 and 55.0 mol.% of isophthalic acid; d) between 45.0 and 72.0 mol% of a dicarboxylic acid (DA) selected in the group of nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid) and combinations thereof; these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B);
Tg being measured by Differential Scanning Calorimetry (“DSC”) according to ISO 11357.
Claim 2. Polyamide (PA) according to claim 1, wherein the dicarboxylic acid (DA) is decanedioic acid (sebacic acid).
Claim 3. Polyamide (PA) according to claim 1 or claim 2, wherein:
- the diamine component (A) comprises: a) between 85.0 and 95.0 mol% of MACM; b) between 5.0 and 15.0 mol% of PACM; and
- the dicarboxylic acid component (B) comprises: c) between 45.0 and 55.0 mol.% of isophthalic acid; d) between 45.0 and 55.0 mol% of dicarboxylic acid (DA). or wherein:
- the diamine component (A) comprises: a) between 88.0 and 92.0 mol% of MACM; b) between 8.0 and 12.0 mol% of PACM; and
- the dicarboxylic acid component (B) comprises: c) between 48.0 and 52.0 mol.% of isophthalic acid; d) between 48.0 and 52.0 mol% of dicarboxylic acid (DA).
Claim 4. Polyamide (PA) according to any one of the preceding claims, wherein the proportion of MACM in the diamine component (A) is:
- between 87.0 and 93.0 mol%; or
- between 88.0 and 92.0 mol%; or
- between 89.0 and 91.0 mol%; and/or wherein the proportion of PACM in the diamine component (A) is:
- between 7.0 and 13.0 mol%; or
- between 8.0 and 12.0 mol%; or
- between 9.0 and 11.0 mol%.
Claim 5. Polyamide (PA) according to any one of the preceding claims, wherein the diamine component (A) does not comprise any lactam.
Claim 6. Polyamide (PA) according to any one of the preceding claims, wherein the diamine component (A) does not comprise hexamethylene diamine.
Claim 7. Polyamide (PA) according to any one of the preceding claims, wherein the diamine component (A) consists essentially of or consists of MACM and PACM where the expression "consist essentially" means in relation to the diamine component that component (A) consists of MACM, of PACM and up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least one diamine other than MACM and PACM, this proportion in mol% being based on the total amount of diamines in the diamine component (A).
Claim 8. Polyamide (PA) according to any one of the preceding claims, wherein the proportion of isophthalic acid in the dicarboxylic acid component (B) is:
- between 47.0 and 53.0 mol%; or
- between 48.0 and 52.0 mol%; or
- between 49.0 and 51.0 mol%; and/or wherein the proportion of dicarboxylic acid (DA) in the dicarboxylic acid component (B) is:
- between 47.0 and 53.0 mol%; or
- between 48.0 and 52.0 mol%; or
- between 49.0 and 51.0 mol%.
Claim 9. Polyamide (PA) according to any one of the preceding claims, wherein the dicarboxylic acid component (B) does not comprise terephthalic acid.
Claim 10. Polyamide (PA) according to any one of the preceding claims, wherein the dicarboxylic acid component (B) does not comprise dodecanedioic acid.
Claim 11. Polyamide (PA) according to any one of the preceding claims, wherein the dicarboxylic acid component (B) consists essentially of or consists of isophthalic acid and of the dicarboxylic acid (DA), where the expression "consist essentially" means in relation to the dicarboxylic acid component that the dicarboxylic acid component (B) consists of isophthalic acid, of dicarboxylic acid (DA) and up to 2.0 mol%, preferably up to 1.0 mol%, even more preferably up to 0.5 mol%, of at least one dicarboxylic acid other than isophthalic acid and dicarboxylic acid (DA), this proportion in mol% being based on the total amount of the dicarboxylic acids in the dicarboxylic acid component (B).
Claim 12. Polyamide (PA), notably according to any one of the preceding claims, comprising the recurring units (RPAI) and (RPA2), where (RPAI) is represented by formula (I): and where (RPA2) is represented by (Ila) and/or
(Ilb), preferably (RPA2) is represented by (Ila), where the substituents Xi and X2 on the cyclohexane rings are either both Me or both H and wherein the proportions of these recurring units are the following:
- (RPAI): between 28.0 and 55.0 mol%;
- (RPA2): between 45.0 and 72.0 mol%; and wherein the proportions of these substituents Me and H in the polyamide (PA) are the following: between 48.0 and 95.0 mol% of Me; and between 5.0 and 52.0 mol% of H.
Claim 13. Polyamide (PA) according to claim 12, wherein the proportions of the substituents Me and H in the polyamide (PA) are the following: between 85.0 and 95.0 mol% of Me; and between 5.0 and 15.0 mol% of H.
Claim 14. Polyamide (PA) according to claim 12 or claim 13, wherein the proportions of the recurring units are the following:
- (RPAI): between 45.0 and 55.0 mol%
- (RPA2): between 45.0 and 55.0 mol%
Claim 15. Polyamide (PA) according to any one of the preceding claims, wherein the polyamide (PA) does not comprise any recurring unit derived from a lactam or from an aminoacid.
Claim 16. Polyamide (PA) according to any one of the preceding claims, wherein the polyamide (PA) does not comprise any recurring unit derived from hexamethylenediamine.
Claim 17. Polyamide (PA) according to any one of the preceding claims, wherein the polyamide (PA) does not comprise any recurring unit derived from terephthalic acid.
Claim 18. Polyamide (PA) according to any one of the preceding claims, wherein the polyamide (PA) does not comprise any recurring unit derived from dodecanedioic diacid.
Claim 19. Polyamide (PA) according to any one of the preceding claims, wherein the recurring units of polyamide (PA) consist essentially in or consist in recurring units (RPAI) and (RPA2), the expression "consist essentially" means in relation to the recurring units means that the recurring units of polyamide (PA) consist of recurring units (RPAI), (RPA2) and up to 2.0 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol% of recurring units other than (RPAI) and (RPA2).
Claim 20. Polyamide (PA) according to any one of the preceding claims, wherein the polyamide (PA) is amorphous, notably exhibiting a heat of fusion (Hm) of at most 5.0 J/g, preferably at most 2.0 J/g, where Hm is measured by Differential Scanning Calorimetry (“DSC”) according to ISO 11357, notably using a heating and cooling rate of 20°C/min.
Claim 21. Polyamide (PA) according to any one of the preceding claims, exhibiting an aromatic content lower than 11.0 wt%, preferably lower than 10.0 wt%.
Claim 22. Polyamide (PA) according to any one of the preceding claims, exhibiting a bio content of at least 20.0%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.
Claim 23. Polyamide (PA) according to any one of the preceding claims, exhibiting a Tg of at least 200°C, preferably at least 201 °C, Tg being measured by Differential Scanning Calorimetry (“DSC”) according to ISO 11357, notably using a heating and cooling rate of 20°C/min.
Claim 24. Polyamide (PA) according to any one of the preceding claims, exhibiting a number average molecular weight ("Mn") of at least 10,000 g/mol, Mn being determined using the following equation (1): Mn = 2,000,000 / [EG] (1) wherein [EG] is the proportion of end- groups in the PA expressed in mmol/kg.
Claim 25. Polyamide (PA) according to any one of the preceding claims, exhibiting a tensile modulus measured according to ASTM D638 of at least 2.0 GPa.
Claim 26. Polyamide (PA) according to any one of the preceding claims, exhibiting a tensile strength measured according to ASTM D638 of at least 80.0 MPa.
Claim 27. Polyamide (PA) according to any one of the preceding claims, exhibiting an elongation at break measured according to ASTM D638 of at least 12.0%.
Claim 28. Polyamide (PA) according to any one of the preceding claims, exhibiting an izod impact energy measured according to ASTM D256 of at least 65.0 J/m.
Claim 29. Polyamide (PA) according to any one of the preceding claims, exhibiting a transparency of at least 90.0%, preferably at least 95.0% when measured according to ASTM DI 003 on an injection moulded specimen of 3.2 or of 2.5 mm thickness.
Claim 30. Polyamide (PA) according to any one of the preceding claims, exhibiting a haze measured according to ASTM DI 003 on an injection moulded specimen of 3.2 or of 2.5 mm thickness is usually lower than 8.0%, preferably lower than 5.0%, preferably lower than 2.0%.
Claim 31. Polyamide (PA) according to any one of the preceding claims, wherein the end- groups in the polyamide are selected in the group of -NEE, -COOH and amide end-groups.
Claim 32. Polyamide (PA) according to claim 32, wherein the amide end-groups are of formula -NH-C(=O)-R where R is an an alkyl group, an aryl group or a cycloalkyl group and/or of formula -C(=O)-NH-R' where R' is an alkyl group or a cycloalkyl group.
Claim 33. Polyamide (PA) according to any one of the preceding claims, wherein the PACM monomer used for the preparation of polyamide (PA) comprises a proportion of (trans, trans)- 4,4'-methylene bisfcyclohexylamine] between 15.0 and 25.0 mol%, this proportion being relative to the contents of the three isomers.
Claim 34. Polyamide (PA) according to any one of the preceding claims, prepared by polycondensation by heating a reaction mixture (RM) comprising all the monomers, the reaction mixture (RM) notably comprising or consisting of:
- MACM, PACM, isophthalic acid and dicarboxylic acid (DA) selected in the group of azelaic acid, sebacic acid and combinations thereof; preferably the dicarboxylic acid (DA) being sebacic acid;
- optionally a catalyst, notably selected in the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite, such as sodium hypophosphite and phenylphosphinic acid, and combination thereof;
- optionally at least one end-capping agent selected in the group of monocarboxylic acids, primary amines and combination thereof;
- optionally water, the proportion of which is less than 60 wt.% of water, preferentially less than 30 wt.%, less than 20 wt.%, less than 10 wt.%, preferentially with no added water, this proportion is given based on the total weight of the reaction mixture (RM).
Claim 35. Polyamide (PA) according to any one of the preceding claims, prepared from biobased azelaic acid and/or sebacic acid exhibiting a bio content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.
Claim 36. Polyamide (PA) according to any one of the preceding claims, prepared from MACM and/or PACM exhibiting a bio content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.
Claim 37. Polyamide (PA) according to any one of the preceding claims, prepared from isophthalic acid exhibiting a bio content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.
Claim 38. Polyamide (PA) according to any one of the preceding claims, exhibiting a water uptake at 23 °C lower than 5.0 wt%, preferably lower than 3.5 wt%, the water uptake at 23 °C being determined by (i) providing a specimen shaped according to ISO527 in its dry state (moisture content of less than 0.2 wt.%), (ii) immersing the same in deionized water at 23°C, until reaching a constant weight, (iii) calculating the water uptake with the formula:
Water uptake wherein
Wbefore is the weight of the shaped specimen in its original dry state and Waiter is the weight of the shaped specimen after water uptake.
Claim 39. Polymer composition (C) comprising: at least one polyamide (PA) as disclosed in any one of claims 1-38; at least one polymer additive selected in the group consisting of heat stabilizers, UV stabilizers, colorants, antistatic agents and combination of two or more of said additives;
- the polymer(s) and the polymer additive(s) of the polymer composition (C) being preferably blended.
Claim 40. Polymer composition (C) according to claim 39, wherein the proportion of the polymer additive(s) is between 0.1 and 10.0 wt%.
Claim 41. Polymer composition (C) according to claim 39 or 40, exhibiting a tensile modulus measured according to ASTM D638 of at least 2.0 GPa.
Claim 42. Polymer composition (C) according to any one of claims 39-41, exhibiting a tensile strength measured according to ASTM D638 of at least 80.0 MPa.
Claim 43. Polymer composition (C) according to any one of claims 39-42, exhibiting an elongation at break measured according to ASTM D638 of at least 12.0%.
Claim 44. Polymer composition (C) according to any one of claims 39-43, exhibiting an izod impact energy measured according to ASTM D256 of at least 65.0 J/m.
Claim 45. Polymer composition (C) according to any one of claims 39-44, exhibiting a transparency of at least 90.0%, preferably at least 95.0% when measured according to ASTM D1003 on an injection moulded specimen of 3.2 mm or of 2.5 mm thickness.
Claim 46. Polymer composition (C) according to any one of claims 39-45, exhibiting a haze measured according to ASTM D1003 on injection moulded specimens of 3.2 mm or of 2.5 mm thickness which is lower than 8.0%, preferably lower than 5.0%, preferably lower than 2.0%.
Claim 47. Use of the polyamide (PA) according to any one of claims 1-38 or the polymer composition according to any one of claims 39-46 for the preparation of a transparent article.
Claim 48. Container, notably a transparent container, made of polyamide (PA) as defined in any one of claims 1-38 or of the polymer composition (C) as defined in any one of claims 39- 46.
EP23837176.9A 2022-11-28 2023-11-20 Bio based transparent polyamides Pending EP4626949A1 (en)

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DE69405623T2 (en) 1993-03-30 1998-01-29 Air Prod & Chem Process for the preparation of cyclohexylamines by catalytic hydrogenation of anilines
US6277911B1 (en) 1995-02-01 2001-08-21 Ems Inventa Ag Transparent, colorless, amorphous copolyamides and molded articles made therefrom
CA2162430A1 (en) 1995-02-01 1996-08-02 Ems-Inventa Ag Transparent, colorless, amorphous polyamides and molded articles
EP1595907A1 (en) 2004-05-14 2005-11-16 Arkema Transparent amorphous polyamides based on diamines and on tetradecanedioic acid
US20050272908A1 (en) 2004-05-14 2005-12-08 Annett Linemann Transparent amorphous polyamides based on diamines and on tetradecanedioic acid
BRPI0621292B1 (en) 2006-01-31 2017-06-06 Ems-Chemie Ag copolyamide molding material, and use thereof for the production of transparent, overheated steam sterilizable and extruded castings
EP2666803B1 (en) 2012-05-23 2018-09-05 Ems-Patent Ag Scratch-proof, transparent and ductile copolyamide moulding materials, moulded parts produced from same and use of same
US9499465B2 (en) 2013-03-15 2016-11-22 Board Of Trustees Of Michigan State University Synthesis of biobased and substituted terephthalic acids and isophthalic acids
EP4008743B1 (en) 2020-12-04 2024-09-04 Ems-Chemie Ag Water vapour-resistant transparent polyamides
EP4067409A1 (en) 2021-04-01 2022-10-05 Ems-Chemie Ag Renewable cycloaliphatic diamines and polymers thereof

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