High melting temperature soluble semi-crystalline polyamides

Abstract

This invention relates to (co)polyamides comprising at least 85 mol% (mol.%) of repeating units (R) having formula (I). PA (I) The present invention also relates to polymer compositions comprising such (co)polyamides, articles comprising such compositions, and methods of using said articles in high-temperature applications requiring sufficient swelling or deformation upon exposure to moisture, such as in oil and gas extraction processes (e.g., fracturing balls), or as support materials for printing three-dimensional (3D) parts.

Description

Technical Field

[0001] The present invention relates to (co)polyamide as disclosed in claim 1. Background Technology

[0002] (Co)polyamides with high melting temperatures (e.g., above 300°C) are known and described in the literature. Notably, this type of polyamide is produced by Solvay Specialty Polymers USA under the trade name... PPA is known. These polyamides also exhibit low water absorption, which is a useful advantage in many applications, notably due to the resulting strength and stiffness stability, even at high levels of humidity.

[0003] However, in some applications, such as those described below, there is a need for (co)polyamides that exhibit high melting temperatures while simultaneously possessing the ability to dissolve upon immersion in an aqueous medium. For example, in the fabrication of 3D parts by depositing layers of part material, support layers or structures are typically constructed beneath or within cavities of the overhanging portions of the 3D part being built, parts not supported by the part material itself. The same deposition techniques used to deposit the part material can be employed to construct these support structures. The host computer generates additional geometry that acts as support structures for the overhanging or free-space segments of the 3D part being formed, and in some cases, as support structures for the sidewalls of the 3D part being formed. The support material adheres to the part material during manufacturing and can be removed from the completed 3D part when the printing process is complete. Typically, soluble / leachy materials are preferred as support materials, so that the support parts can be dissolved from the final 3D part once it has been built, making post-treatment processes such as soaking and rinsing effective for recycling the part. Unlike supports that can only be mechanically removed, the use of soluble supports allows for increased design freedom for parts while maintaining a pleasing surface finish. Soluble / water-swellable and / or printable materials have been described in the field, including polyamide support materials. For example, WO 2017 / 167691(D3) (Solvay Specialty Polymers USA, LLC) relates to a method for manufacturing 3D articles using a semi-crystalline polyamide as a support material, which has sufficient water absorption to provide significant swelling and deformation in order to ensure separation from the target 3D part. Among suitable polyamides, reference is made to polyamides obtainable from the condensation of certain diacids with certain diamines, including N-methyl-bis-hexamethylene-triamine. Similarly, US2019 / 0160732 teaches a soluble polyamide that can be used as a support material in 3D printing technology, comprising units from a hydrophilic monomer, units from a hydrophobic dicarboxylic acid monomer, and units from a hydrophobic amine monomer, wherein the hydrophilic monomer unit may include a primary amine group, a secondary amine group, a tertiary amine group, a quaternary ammonium salt, an oxyethylidene group, a hydroxyl group, a carboxyl group, a carboxyl salt group, a phosphate group, a phosphate ester group, a sulfonic acid group, or a sulfonate ester group. Furthermore, WO 2017 / 167692 (Solvay Specialty Polymers, LLC) teaches (co)polyamides containing more than 60 moles of repeating units of a condensation of a diamine derived from 1,4-cyclohexanedicarboxylic acid and having the formula H2N-(CH2)2-O-(CH2)2-O-(CH2)2-NH2, having a melting point exceeding 260°C and being endowed with sufficient solubility in water, acidic or alkaline water at temperatures exceeding 50°C, and are described as suitable as support materials for printed 3D parts.These (co)polyamides may additionally contain other units, such as units derived from aromatic diacids and / or units derived from aliphatic diamines; among these latter, N,N-bis(3-aminopropyl)methylamine is noteworthy.

[0004] However, the selection of water-soluble polymers remains relatively limited and the water-soluble polymer materials taught may not be sufficient to support the printing of certain polymers that require high processing temperatures. Furthermore, in some cases, the soaking / rinsing separation technique remains very cumbersome, at least because it requires high-temperature dissolution of large amounts of wastewater and extensive post-treatment (due to low solubility) to dispose of and / or recover the water-soluble support polymer.

[0005] As explained above, in the manufacture of 3D parts using high-temperature component materials such as polysulfone, polyethersulfone, polyphenylsulfone, polyaryletherketone, polyetherimide, polyamideimide, polyphthalamide, and polyphenylene sulfide, support materials are required to provide vertical and / or lateral support under the higher operating conditions required by the high-temperature component materials. Furthermore, the support materials should not soften too much under these higher operating conditions; otherwise, deformation would render them ineffective as support structure materials.

[0006] The applicant's achievement is the unexpected identification of the structural requirements of (co)polyamides that exhibit such advantageous properties. More specifically, the applicant has now discovered that the (co)polyamides of the present invention enable the simultaneous provision of high melting temperature behavior to effectively serve as solid support materials in printing chambers operating at temperatures exceeding 200°C, while also possessing rapid and high solubility in water-based media, thereby facilitating easy dissolution and recycling.

[0007] Several prior art documents relate to polyamides obtained by the condensation of amines having tertiary amine groups.

[0008] GB 1281547 discloses fiber-forming compositions comprising a polyester and a polyamide containing a basic nitrogen-containing group, such as a diamine having any one of the following formulas:

[0009]

[0010] With dicarboxylic acids having the formula HOOC-Y-COOH (where Y is -(CH2)). p -(p is at least 4) or -(CH2) a -Z-(CH2) b - (where Z is m-phenylene or p-phenylene)) condensation polyamide, the fiber-forming composition being used to formulate polyester dyeable fiber-forming formulations.

[0011] US2016 / 108174 relates to polyamides obtained by polymerization of at least one or more alkyl-BHT diamines and one or more polycarboxylic acids, wherein the alkyl-BHT diamine is selected from methyl-bis(hexamethylenetriamine), ethyl-bis(hexamethylenetriamine), n-propyl-bis(hexamethylenetriamine), and / or isopropyl-bis(hexamethylenetriamine). Among the polycarboxylic acids, cycloaliphatic dicarboxylic acids comprising at least one carbon ring having from 4 to 8 carbon atoms on the ring are noteworthy, such as cyclohexanedicarboxylic acids, particularly 1,2-cyclohexanedicarboxylic acids, 1,3-cyclohexanedicarboxylic acids, and 1,4-cyclohexanedicarboxylic acids, and 2,5-tetrahydrofurandicarboxylic acids.

[0012] JP 2018 / 116084(D1) discloses a polyamide for use as a photoresist. D1 does not disclose the polyamide of the present invention.

[0013] US2018 / 0236804(D2) describes a water-soluble or water-dispersible polyamide suitable for use in photosensitive compositions for manufacturing letterpress printing masterpieces, comprising from 30 to 90 mol of a unit having an alicyclic moiety derived from an alicyclic diamine or an alicyclic diacid, wherein the alicyclic diamine may be 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, norbornyldiamine, 1,4-bis(3-aminopropyl)piperazine, and N-(2-aminoethyl)piperazine, and wherein the alicyclic diacid may be isophorone dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2,3-norbornane-dicarboxylic acid, and 1,3-cyclohexane dicarboxylic acid. Several exemplary embodiments represent polyamides comprising units derived from 1,4-cyclohexanedicarboxylic acid and diamines (such as 1,4-bis(3-aminopropyl)piperazine or methylimino-bis-propionamide) in combination with significant amounts of other units, such as units derived from ε-caprolactam or ω-dodecanolactam, or units derived from bisacylcarboxylic acid and another diamine, resulting in amorphous polyamides having a target transparency for photogravure printing processes.

[0014] Notably, Example 8 of US2018 / 0236804 provides an amorphous copolyamide obtained by polycondensation of ε-caprolactam (15 mol.%), 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) (42.1 mol.%), and 1,4-bis(aminopropyl)piperazine (BAPP) (42.9 mol.%), thereby producing a copolyamide having about 25 mol.% repeating units of the formula -C(O)-(CH2)5-NH- and about 75 mol.% units of the following formula: Similarly, Example 11 provides an amorphous copolyamide obtained by polycondensation of ε-caprolactam (15 mol.%), 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) (42.1 mol.%), and methyl-bis(hexamethylenetriamine) (MeBHT) (42.9 mol.%), thereby producing a copolyamide having about 25 mol.% repeating units of the formula -C(O)-(CH2)5-NH- and about 75 mol.% units of the following formula: Finally, Example 17 provides an amorphous copolyamide obtained by polycondensation of adipic acid (7.5 mol.%), 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) (42.1 mol.%), 1,4-bis(aminopropyl)piperazine (BAPP) (42.9 mol.%), and hexamethylenediamine (7.5 mol.%), thereby producing a product having approximately 72 mol.% of the product with the formula... Copolyamides with repeating units.

[0015] None of the documents listed above describe the (co)polyamide of claim 1. The applicant has unexpectedly discovered that the polyamide (A) according to the invention not only exhibits a high melting temperature (i.e., exceeding 260°C), but also possesses significant solubility (above 30% wt / wt) in mildly acidic aqueous compositions (e.g., 5% wt. acetic acid in water) at room temperature. These technical features enable its use not only in high-temperature applications or applications requiring sufficient swelling or deformation upon exposure to moisture, but also in applications requiring both high-temperature resistance and sufficient swelling or deformation upon exposure to moisture (e.g., oil and gas extraction, 3D printing). Summary of the Invention

[0016] The present invention relates to (co)polyamide as disclosed in claim 1.

[0017] The applicant has discovered that the alicyclic moiety of the selected diacid portion... The specific combination of tertiary amine-containing moieties connected by non-sterically hindered -CH2- bridges of the amine moieties, plus the absence of different units in limited presence (<15 mol.%), provides a polyamide (A) with the ability to crystallize in a regular lattice to achieve a high melting temperature. At the same time, the presence of tertiary amine groups provides easily accessible ionizable sites, which significantly contributes to providing solubility in slightly acidic aqueous media.

[0018] When used in connection with the (co)polyamides of the present invention, the term "repeating unit" is intended to indicate a unit derived from the condensation of diamines and diacids having the following formula (AABB), or a unit derived from the condensation of amino acids or lactams having the following formula (AB):

[0019] -NR H -RAB -C(O)-(AB)

[0020] -NR H -R BB -NR H -C(O)-R AA -C(O)-(AABB)

[0021] Where R H It is a hydrogen or hydrocarbon group; and R AB R BB R AA They may be the same or different from each other, and are divalent hydrocarbon groups, which may contain one or more heteroatoms.

[0022] Repeating unit (R) with equation (I) PA ) is an example of a unit having the formula (AABB).

[0023] The terms “(co)polyamide” or “polyamide” are used herein to indicate:

[0024] - Homopolymer, essentially containing 100 mol.% of repeating units (R) of formula (I). PA ),and

[0025] - Copolyamide, comprising at least about 95 mol.% of repeating units (R) having formula (I). PA The molar percentage is given relative to the total number of repeating units of the (co)polyamide [polyamide (A)]. The copolyamide may contain, for example, at least about 96 mol.%, at least about 97 mol.%, at least about 98 mol.%, or at least about 99 mol.%.

[0026] The above repeating unit (R) with equation (I) PA It is obtained by polycondensation of a mixture of a dicarboxylic acid component consisting of one or more 1,4-cyclohexanedicarboxylic acids [acid (CHDA)] (or derivatives thereof) and a diamine component consisting of one or more diamines having any one of the following formulas (or derivatives thereof): [amine(N] N 1 )] [amine(N] N 2 )]:

[0027] Where R alk ° is a monovalent C1-C6 alkyl group; R alk 1 and R alk 2 Each of them, whether identical or different, is a bond or a divalent C1-C bond. 12Alkylenes, which may contain one or more N atoms, provided that R is an alkylene group. alk 1 and R alk 2 They are not both keys, and R is a key. alk 1 and R alk 2 Together with the nitrogen atoms they are attached to, they form heterocyclic mononuclear or polynuclear groups; and

[0028] -n1 and n2 are either the same or different from each other and are integers from 1 to 12 each time they appear.

[0029] Notably, acid (CHDA) derivatives include salts, anhydrides, esters, and acyl halides, which can form amide groups; similarly, amines (N... N 1 ) and (N N 2 The derivatives notably include their salts, which can also form amide groups.

[0030] The expression “one or more 1,4-cyclohexanedicarboxylic acid” associated with acid (CHDA) means including diastereomeric pure cis or trans diastereomers and mixtures thereof, in any proportion. Typically, a mixture of cis and trans diastereomers of acid (CHDA) is used.

[0031] Repeating unit (R) with equation (I) PA Choose a group consisting of the following items:

[0032] - The unit (R) with the following formula PA 1 ): Where p and q may be the same or different from each other, and are independent integers from 3 to 9, preferably from 4 to 6, and most preferably each of p and q is 6; R H It is a monovalent C1-C6 alkyl group, specifically selected from the group consisting of: methyl, ethyl, propyl (including isopropyl and n-propyl); and

[0033] - The unit (R) disclosed in claim 1 PA 2 ).

[0034] Unit (R) PA 1 Specific instances of ) are noteworthy for those where each of p and q equals 6, that is, those with the following expression: Where R BH It is a C1-C3 alkyl group, particularly selected from the group consisting of: methyl, ethyl, and propyl (isopropyl, n-propyl). These preferred units (R)PA 1 It is obtained by polycondensation of a mixture of a dicarboxylic acid component consisting of one or more 1,4-cyclohexanedicarboxylic acids [acid (CHDA)] (or derivatives thereof) and a diamine component, wherein the diamine component consists of methyl-bis(hexamethylenetriamine), ethyl-bis(hexamethylenetriamine), n-propyl-bis(hexamethylenetriamine), isopropyl-bis(hexamethylenetriamine), or mixtures thereof, most preferably methyl-bis(hexamethylenetriamine) (i.e., having the formula as described above, wherein R...). BH (It is methyl).

[0035] The unit (R) of claim 1 PA 2 (Selected from:)

[0036] - Units with the following formula:

[0037] Where r and s are either the same or different from each other, and are independent integers from 1 to 3;

[0038] - Units with the following formula:

[0039] Where r and s are either the same or different from each other, and are independent integers from 1 to 3;

[0040] - Units with the following formula:

[0041] Where r and s are either the same or different from each other, and are independent integers from 1 to 3;

[0042] - Wherein the azacyclic alkane is one of the 1,3-diazacyclohexane rings, such as those having units of the following formula: Where r and s are either the same or different from each other, and are independent integers from 1 to 3;

[0043] - Wherein the azacyclic alkane is 1,4-diazacyclic heptane, such as those having units with the following formula: Where r and s are either the same or different from each other, and are independent integers from 1 to 3;

[0044] - Wherein the azacyclic alkane is one of those with a 1,3,5,7-tetraazacyclic octane ring, such as those having a unit with the following formula:

[0045]

[0046] Wherein Ro is H or C1-C3 alkyl, and r and s are the same or different from each other, and are independent integers from 1 to 3;

[0047] - Units with the following formula:

[0048]

[0049] Wherein Rt is H or C1-C3 alkyl, and r and s are the same or different from each other, and are independent integers from 1 to 3.

[0050] Unit (R) PA 2 The most preferred embodiments are those units, wherein the azacycloalkane is a 1,4-diazacyclohexane ring, i.e., units having the following formula: Where r and s are either the same or different from each other, and are independent integers from 1 to 3.

[0051] These preferred units (R) PA 2 It is usually obtained by polycondensation of a mixture of a dicarboxylic acid component consisting of one or more 1,4-cyclohexanedicarboxylic acids [acid (CHDA)] (or derivatives thereof) and a diamine component consisting of one or more 1,4-bis(aminoalkyl)piperazine, wherein the aminoalkyl group is selected from aminomethyl, aminoethyl and aminopropyl groups.

[0052] A particularly preferred embodiment is a unit (R) having the following formula PA 2 ): This unit is obtained by polycondensation of a mixture of a dicarboxylic acid component consisting of one or more 1,4-cyclohexanedicarboxylic acids [acid (CHDA)] (or derivatives thereof) and a diamine component consisting of 1,4-bis(3-aminopropyl)piperazine.

[0053] As described, the polyamide (A) may contain at most 5 mol.%, notably at most 4 mol.%, at most 3 mol.%, at most 2 mol.%, or at most 1 mol.% of repeating units relative to the total molar percentage of repeating units of the polyamide (A), which are different from those of formula (F) given in the claims, and which conform to any of the following formulas:

[0054] -NR” H -R 1 -C(O)-(II)

[0055] -NR'” H -R 2 -NR'” H -C(O)-R 3 -C(O)-(III)

[0056] Among them, R” H and R'” H They are the same or different from each other and, each time they appear, are H or hydrocarbon groups; and R 1 R 2 R 3They may be the same or different from each other, are divalent hydrocarbon groups, and can be aliphatic, alicyclic, cycloaliphatic, aromatic, or a combination thereof, wherein R 1 R 2 R 3 It may contain one or more heteroatoms selected from the group consisting of O, N, S, and P.

[0057] Specifically, the repeating units (II) and (III) that are different from the unit of formula (F) can be condensation products of at least one mixture selected from the following:

[0058] - A mixture (M1) comprising at least one diacid [acid (DA)] (or a derivative thereof) and at least one diamine [amine (NN)] (or a derivative thereof), wherein (i) the acid (DA) is not an acid (CHDA) and / or (ii) the amine (NN) is not an amine (N) N 1 It is not an amine (N) N 2 );

[0059] - A mixture (M2) containing at least one lactam [lactam (L)];

[0060] - A mixture (M3) containing at least one aminocarboxylic acid [amino acid (AN)]; and

[0061] - Its combination.

[0062] Similarly, as described above, acid (DA) derivatives notably include salts, acid anhydrides, esters, and acyl halides that can form amide groups; similarly, amine (NN) derivatives notably include their salts that can also form amide groups.

[0063] The acid (DA) can be an aromatic dicarboxylic acid [acid (AR)] containing two reactive carboxylic acid groups or an aliphatic dicarboxylic acid [acid (AL)] containing two reactive carboxylic acid groups. For the purposes of this invention, a dicarboxylic acid is considered "aromatic" when it contains one or more aromatic groups.

[0064] Notable non-limiting examples of acids (AR) include phthalic acid (including isophthalic acid (IA) and terephthalic acid (TA)), 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, bis(4-carboxyphenyl)methane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)one, and 4,4'-bis(4 2,2-Carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, bis(3-carboxyphenyl)methane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)one, bis(3-carboxyphenoxy)benzene, naphthalene dicarboxylic acids (including 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid) and biphenyl-4,4'-dicarboxylic acid.

[0065] Among acids (AL), noteworthy examples include oxalic acid (HOOC-COOH), malonic acid (HOOC-CH2-COOH), succinic acid [HOOC-(CH2)2-COOH], glutaric acid [HOOC-(CH2)3-COOH], 2,2-dimethyl-glutaric acid [HOOC-C(CH3)2-(CH2)2-COOH], adipic acid [HOOC-(CH2)4-COOH], 2,4,4-trimethyl-adipic acid [HOOC-CH(CH3)-CH2-C(CH3)2-CH2-COOH], and pimelic acid [HOOC-(CH2)2-COOH]. 5- [COOH], octanoic acid [HOOC-(CH2)6-COOH], azelaic acid [HOOC-(CH2)7-COOH], sebacic acid [HOOC-(CH2)8-COOH], undecanoic acid [HOOC-(CH2)9-COOH], dodecanoic acid [HOOC-(CH2)6-COOH] 10 -COOH], tridecanoic acid [HOOC-(CH2] 11 -COOH], tetradecanoic acid [HOOC-(CH2] 12 -COOH], octadecanoic acid [HOOC-(CH2] 16 -COOH].

[0066] However, the acids that can be used (AL) include acids containing cyclic aliphatic groups, notably including 1,3-cyclohexanedicarboxylic acid, as cis or trans diastereomers, possibly in mixtures.

[0067] According to certain embodiments, acids (DA) [acids (IDA)] containing ionizable groups can be used as condensation monomers of polyamide (A); among these ionizable groups, phenolic hydroxyl, sulfonic acid (typically aromatic sulfonic acid), phosphonic acid, ononyl (including phosphonic and ammonium groups) and the like are noteworthy. Non-limiting examples of this type of acid (IDA) that can be used within the framework of this invention are noteworthy 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 4,6-dihydroxyisophthalic acid, 5-sulfoisophthalic acid (and its salts, such as Li, K, Na, Ag salts), and 2-sulfoterephthalic acid (and its salts, such as Li, K, Na, Ag salts).

[0068] Acids including ionizable groups (IDA) can be used in combination with acids (AR) and / or acids (AL) as detailed above.

[0069] This amine (NN) is usually selected from the group consisting of the following: aliphatic diamines (NN) al ), aromatic diamines (NN) ar ) and its mixtures.

[0070] The diamine (NN) al Typically, it is an aliphatic diamine with 2 to 18 carbon atoms.

[0071] The diamine (NN) alAdvantageously selected from the group consisting of: 1,2-diaminoethane, 1,2-diaminopropane, propylene-1,3-diamine, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,5-diamino-2-methylpentane, 1,4-diamino-1,1-dimethylbutane, 1,4-diamino-1-ethylbutane, 1,4-diamino-1,2-dimethylbutane, 1,4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-diethyl ...amino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4-diamino-1,4 Methylbutane, 1,4-diamino-2,3-dimethylbutane, 1,2-diamino-1-butylethane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,6-diamino-2,5-dimethylhexane, 1,6-diamino-2,4-dimethylhexane, 1,6-diamino-3,3-dimethylhexane, 1,6-diamino-2,2-dimethylhexane, 1,9-diaminononane, 1,6-diamino-2,2,4-trimethylhexane, 1, 6-Diamino-2,4,4-trimethylhexane, 1,7-diamino-2,3-dimethylheptane, 1,7-diamino-2,4-dimethylheptane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-2,2-dimethylheptane, 1,10-diaminodecane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino-1,4-dimethyloctane, 1,8-diamino-2,4-dimethyloctane, 1,8-diamino-3,4-dimethyloctane, 1,8-Diamino-4,5-dimethyloctane, 1,8-diamino-2,2-dimethyloctane, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-4,4-dimethyloctane, 1,6-diamino-2,4-diethylhexane, 1,9-diamino-5-methylnonane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 2,5-bis(aminomethyl)tetrahydrofuran, and N-methyl-bis-hexamethylene-triamine.

[0072] The diamine (NN) al Preferably, the aliphatic alkylene diamine comprises at least one diamine selected from the group consisting of: 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, and mixtures thereof. More preferably, the aliphatic alkylene diamine comprises at least one diamine selected from the group consisting of: 1,6-diaminohexane, 1,10-diaminodecane, and mixtures thereof. Even more preferably, the aliphatic alkylene diamine is 1,6-diaminohexane.

[0073] The diamine (NN) arPreferably, it is selected from the group consisting of: m-phenylenediamine, m-phenylenedimethyldiamine and p-phenylenedimethyldiamine, 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diaminodiphenyl ether (4,4'-ODA), p-phenylenedimethyldiamine (PXDA) and m-phenylenedimethyldiamine (MXDA).

[0074] According to other embodiments, at least one of the amines (NN) is a cyclic aliphatic diamine, i.e., a diamine [amine (cNN)] containing a cyclic aliphatic group; the amine (cNN) is generally selected from the group consisting of: isophorone diamine, 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, p-bis(aminocyclohexyl)methane, isopropylidene di(cyclohexylamine), 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-diaminocyclohexane.

[0075] According to certain other embodiments, at least one amine (NN) [amine (NNE)] containing an ether bond can be used as the polycondensation monomer of polyamide (A); exemplary embodiments of the amine (NNE) (also referred to as polyether diamine) notably include diamines having a portion having the following formula: -(OCH2-CHR) J ) n -, where R J It is an H or C1-C3 alkyl group, preferably -CH3, and n is an integer from 1 to 15, and includes a diamine having a portion having the following formula: -OC(R' J (R) J )-O-, where R' J and R” J They may be the same as or different from each other and, each time they appear, they are H or C1-C3 alkyl groups, preferably -CH3.

[0076] An exemplary embodiment is an amine (NNE) having any of the following formulas: 1)

[0078] Where x and z are zero or integers, and y is an integer, provided that x + y + z is an integer from 1 to 15; 2)

[0080] Where q is an integer from 1 to 15; 3)

[0082] Each x is either the same as or different from the others, and is an integer from 1 to 6; 4)

[0084] Wherein R* and R'* are the same or different from each other, and are independently hydrogen or C1-C3 alkyl; A is alkyl, alkenyl, alkenene, alkylene-heteroalkylene, alkylene-heterocyclic-alkylene, alkylene, alkylene-oxyalkylene, 1,4-alkyl-substituted piperazine, carbonyl, thiocarbonyl; B is alkyl, alkenyl, alkenene, alkylene-heteroalkylene, alkylene-heterocyclic-alkylene, alkylene, alkylene-oxyalkylene, 1,4-alkyl-substituted piperazine, carbonyl, thiocarbonyl; R2 is hydrogen, alkyl, aminoalkyl, alkyl-aminoalkyl, cycloalkyl, heterocyclic alkyl, alkenyl, aryl, or heteroaryl; amines conforming to this structural formula are notably disclosed in WO 2013 / 007128 (Advanced Materials Wuxi Co., Ltd.) 1 / 17 / 2013.

[0085] The lactam (L) suitable for manufacturing polyamide (A) can be any one of β-lactam or ε-caprolactam, dodecalactam.

[0086] Suitable amino acids (AN) for the manufacture of polyamide (A) can be selected from the group consisting of: 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecanoic acid.

[0087] Still within the scope of this invention is the addition of one or more polyfunctional acid / amine monomers comprising more than two carboxylic acid and amine groups to any of the mixtures (M1), (M2), (M3), and combinations thereof. These polyfunctional acid / amine monomers are, for example, polycarboxylic acids having three or more carboxylic acid groups, polyamines having three or more amine groups (e.g., polyamines comprising both primary and secondary amine groups), polyfunctional diacids comprising two carboxylic acid groups and one or more amine groups, and polyfunctional diamines comprising two amine groups and one or more carboxylic acid groups. The combination of said polyfunctional acid / amine monomers generally results in branched structures, star-shaped or dendritic, as notably those described in WO 97 / 24388 (NYLTECHITALIA) 10 / 7 / 1997 and WO 99 / 64496 (NYLTECHITALIA) 12 / 16 / 1999.

[0088] However, for polyamide (A), it is preferred to use repeating units (R) having formula (I). PAThe polymer (A) is selected from homopolymers or quasi-homogeneous polymers. When used in association with polyamide (A), the statement "consistently composed of repeating units" means that, in addition to the listed repeating units, very limited amounts (less than 1 mol.%, preferably less than 0.5 mol.%) of end groups, impurities, defects, and other dummy units may also be present in the polymer (A) without significantly affecting the properties of the polyamide (A).

[0089] The polyamide (A) of the present invention can be prepared by any conventional method, for example by thermal polycondensation of a monomer mixture containing at least one acid (CHDA) and an amine (N). N 1 ) and amines (N N 2 It may contain at least one of the mixtures (M1), (M2) and (M3) as described above, and may additionally contain at least one of the mixtures (M1), (M2) and (M3) as described above.

[0090] In the monomer mixture used to manufacture polyamide (A) via a condensation process, the molar ratio n 二酸 / n 二胺 Within the range of 0.8 to 1.2. In the context of this invention, the term "n" is used... 二酸 "This refers to, for example, the total number of moles of diacid species included in a condensation process. Similarly, the term "n" 二胺 "This refers to, for example, the total number of moles of diamine species included in the condensation process. As an example, if the condensation process involves an additional diacid species besides the acid (CHDA), then n..." 二酸 =n 1CHDA +n DA According to the present invention, the molar ratio n 二酸 / n 二胺 It can be in the range between 0.8 and 1.2, between 0.9 and 1.1, between 0.95 and 1.05, or between 0.98 and 1.02.

[0091] The polyamide (A) of the present invention may have a number-average molecular weight M in the range of 1000 g / mol to 50000 g / mol, for example from 2000 g / mol to 40000 g / mol or from 4000 g / mol to 35000 g / mol. N The number-average molecular weight was determined by gel permeation chromatography (GPC) following ASTM D5296 instructions with reference to substantially monodisperse polystyrene standards.

[0092] The polyamide (A) of the present invention is semi-crystalline. “Semi-crystalline” means a polymer having an amorphous phase and a crystalline phase, thus producing a detectable melting point, as determined by differential scanning calorimetry according to ASTM D3418.

[0093] More specifically, the polyamide (A) has a crystallinity such that its heat of fusion is at least 5 J / g, preferably at least 10 J / g, and more preferably at least 15 J / g, when determined by differential scanning calorimetry according to ASTM D3418.

[0094] The polyamide (A) of the present invention advantageously has a melting point of at least about 250°C, as determined according to ASTM D3418. The polyamide (A) of the present invention may have a melting point of, for example, at least about 255°C, at least about 258°C, or at least about 260°C.

[0095] As explained, the semi-crystalline nature of polyamide (A), and most importantly, the presence of a crystalline phase with a melting temperature exceeding 250°C, makes it a material suitable for maintaining structural integrity and mechanical properties in the solid phase at temperatures up to near the melting point. This makes polyamide (A) suitable as a support material for applications that are expected to be exposed to temperatures exceeding 200°C for extended periods.

[0096] Compositions containing polyamide (A)

[0097] Another object of the present invention is a polyamide composition (C) comprising the polyamide (A) of the present invention described above.

[0098] Polyamide (A) may be present in composition (C) in an amount greater than 30 wt.%, greater than 35 wt.%, greater than 40 wt.%, or greater than 45 wt.% based on the total weight of polymer composition (C). (Co)polyamide may be present in composition (C) in an amount less than 95 wt.%, notably less than 90 wt.%, less than 80 wt.%, less than 70 wt.%, or less than 60 wt.% based on the total weight of polymer composition (C).

[0099] Polyamide (A) may be present in composition (C) in an amount, for example, between 35 and 60 wt.% based on the total weight of the polyamide composition (C), such as between 40 and 55 wt.%.

[0100] The composition (C) may also contain a component selected from the group consisting of: reinforcing agents, toughening agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, nucleating agents, crosslinking agents, and antioxidants.

[0101] A variety of selected reinforcing agents (also referred to as reinforcing fibers or reinforcing fillers) may be added to the compositions according to the invention. These may be selected from fibrous reinforcing agents and particulate reinforcing agents. Fibrous reinforcing fillers are considered herein to be materials having a length, width, and thickness, wherein the average length is significantly greater than both the width and thickness. Generally, such materials have an aspect ratio (defined as the average ratio between the length and the largest of the width and thickness) of at least 5, at least 10, at least 20, or at least 50.

[0102] The reinforcing filler can be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fiber, carbon fiber, synthetic polymer fiber, aramid fiber, aluminum fiber, titanium fiber, magnesium fiber, boron carbide fiber, rock wool fiber, steel fiber and wollastonite.

[0103] Among fibrous fillers, glass fibers and carbon fibers are preferred, with carbon fibers being the most preferred; glass fibers include chopped precursor fibers A-, E-, C-, D-, S-, and R-glass fibers, as described in Chapter 5.2.3, pages 43-48 of John Murphy's Additives for Plastics Handbook, 2nd edition. As used herein, the term "carbon fiber" is intended to include graphitized, partially graphitized, and ungraphitized carbon-reinforced fibers or mixtures thereof. Carbon fibers usable in this invention can advantageously be obtained by heat treatment and pyrolysis of various polymer precursors, such as synthetic fibers, polyacrylonitrile (PAN), aromatic polyamides, or phenolic resins; carbon fibers usable in this invention can also be obtained from pitch materials. The term "graphite fiber" is intended to refer to carbon fibers obtained by high-temperature pyrolysis (above 2000°C) of carbon fibers, wherein the carbon atoms are arranged in a manner similar to the structure of graphite. Carbon fibers usable in this invention are preferably selected from the group consisting of: PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof.

[0104] Preferably, the filler is selected from fibrous fillers. More preferably, it is a reinforcing fiber capable of withstanding high-temperature applications.

[0105] The reinforcing agent may be present in the composition (C) in an amount greater than 5 wt.%, notably greater than 10 wt.%, greater than 15 wt.%, greater than 20 wt.%, greater than 25 wt.%, or greater than 30 wt.% by weight based on the total weight of the polymer composition (C). These reinforcing agents may also be present in the composition (C) in an amount less than 65 wt.%, less than 60 wt.%, less than 55 wt.%, or less than 50 wt.% based on the total weight of the polymer composition (C).

[0106] The reinforcing filler may be present in the composition (C) in an amount, for example, between 5 and 60 wt.% of the total weight of the polyamide composition (C), such as between 15 and 50 wt.%.

[0107] The composition (C) of the present invention may further comprise a toughening agent. The toughening agent is typically low glass transition temperature (T0). g ) polymer, wherein T g For example, below room temperature, below 0°C, or even below -25°C. Due to its low T... g Toughening agents are typically elastomers at room temperature. Toughening agents can also be functionalized polymer backbones.

[0108] The polymer backbone of the toughening agent can be selected from elastomer backbones, including polyethylene and its copolymers, such as ethylene-butene; ethylene-octene; polypropylene and its copolymers; polybutene; polyisoprene; ethylene-propylene-rubber (EPR); ethylene-propylene-diene monomer rubber (EPDM); ethylene-acrylate rubber; butadiene-acrylonitrile rubber, ethylene-acrylic acid (EAA), ethylene-vinyl acetate (EVA); acrylonitrile-butadiene-styrene rubber (ABS), block copolymer styrene-ethylene-butadiene-styrene (SEBS); block copolymer styrene-butadiene-styrene (SBS); methacrylate-butadiene-styrene (MBS) type core-shell elastomers, or mixtures of one or more of the above.

[0109] When toughening agents are functionalized, the functionalization of the backbone can be achieved by copolymerization of monomers containing the functionalization, or by grafting a polymer backbone with another component.

[0110] Notable examples of functionalized toughening agents include terpolymers of ethylene, acrylate, and glycidyl methacrylate; copolymers of ethylene and butyl acrylate; copolymers of ethylene, butyl acrylate, and glycidyl methacrylate; ethylene-maleic anhydride copolymers; EPR grafted with maleic anhydride; styrene-maleimide copolymers grafted with maleic anhydride; SEBS copolymers grafted with maleic anhydride; styrene-acrylonitrile copolymers grafted with maleic anhydride; and ABS copolymers grafted with maleic anhydride.

[0111] The toughening agent may be present in the composition (C) in an amount greater than 1 wt.%, greater than 2 wt.%, or greater than 3 wt.% based on the total weight of the composition (C). The toughening agent may be present in the composition (C) in an amount less than 30 wt.%, less than 20 wt.%, less than 15 wt.%, or less than 10 wt.% based on the total weight of the polymer composition (C).

[0112] Composition (C) may also contain other conventional additives commonly used in the art, including plasticizers, colorants, pigments (e.g., black pigments such as carbon black and aniline black), antistatic agents, dyes, lubricants (e.g., linear low-density polyethylene, calcium stearate or magnesium stearate or sodium lignite), heat stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, and polymeric, oligomeric and small molecule crosslinking agents, such as modified styrene-acrylic polymers and oligomers, bisphenol A glycidyl ether and tris(4-hydroxyphenyl)methane triglycidyl ether.

[0113] The composition (C) may also include one or more other polymers, preferably copolyamides different from those of the present invention. It is noteworthy that semi-crystalline or amorphous polyamides, such as aliphatic polyamides, semi-aromatic polyamides, and more generally, polyamides obtained by polycondensation between aromatic or aliphatic saturated diacids and aliphatic saturated or aromatic primary diamines, lactams, amino acids, or mixtures of these different monomers.

[0114] Preparation of composition (C)

[0115] The present invention further relates to a method for preparing the composition (C) as detailed above, the method comprising melt blending polyamide (A) and specific components, such as fillers, toughening agents, stabilizers and any other optional additives.

[0116] In the context of this invention, any melt blending method can be used to mix the polymeric and non-polymeric components. For example, the polymeric and non-polymeric components can be fed into a melt mixer (such as a single-screw or twin-screw extruder, a stirrer, a single-screw or twin-screw kneader, or a Banbury mixer), and this addition step can be either adding all components at once or adding them batch by batch. When adding the polymeric and non-polymeric components batch by batch, a portion of these polymeric and / or non-polymeric components is added first, and then melt-mixed with the subsequently added remaining polymeric and non-polymeric components until a well-mixed composition is obtained. If the reinforcing agent exhibits a long physical shape (e.g., long glass fibers), stretch extrusion molding can be used to prepare the reinforced composition.

[0117] Products

[0118] The present invention also relates to molded articles comprising the polyamide (A) of the present invention described above or the composition (C) of the present invention described above.

[0119] According to an embodiment, an article comprising the polyamide (A) of the present invention or the composition (C) of the present invention is processed in a dry state, and the article has a moisture content of less than 0.5 wt.% or less than 0.2 wt.% relative to the total weight of the article.

[0120] The product may noteworthyly be a disposable downhole tool that is desirably disintegratable when exposed to the wellbore environment; exemplary embodiments of disposable downhole tools noteworthyly be plugs used in well production enhancement / fracking operations, commonly referred to as "fracking plugs", and which typically provide means for holding a ball (commonly referred to as a "facturing ball / frac ball") that acts as a one-way check valve, and a fracturing ball.

[0121] Articles made from the polyamide (A) or composition (C) of the present invention can also be used in the medical field, for example as reabsorbable sutures or dissolvable implants.

[0122] Articles can be molded from the polyamide (A) or composition (C) of the present invention by any method suitable for thermoplastics (e.g., extrusion, injection molding, blow molding, rotational molding or compression molding).

[0123] Articles made from the polyamide (A) or composition (C) of the present invention can also be used in 3D printing processes (e.g., filament fabrication) in the form of filaments or strands.

[0124] Use of polyamide (A) or composition (C) and articles thereof

[0125] The polyamide (A) or composition (C) of the present invention, or any article derived therefrom, can be used in oil and gas extraction applications, for example, for the preparation of articles that exhibit thermal stability at high operating temperatures and sufficient solubility in aqueous media to dissolve when needed (e.g., after fracturing).

[0126] The polyamide (A) or composition (C) of the present invention can also be used as an sizing agent, for example for treating / coating polymer fibers (e.g., polyamide fibers) or carbon fibers.

[0127] The polyamide (A) or composition (C) of the present invention can also be used in the medical field, for example, for the preparation of reabsorbable or soluble materials, such as in the form of sutures or implantable articles.

[0128] The polyamide (A) or composition (C) of the present invention, or any article thereof, can be used as a support material for printed 3D parts.

[0129] Using polyamide (A), composition (C), or any article derived therefrom as a support material, an additive manufacturing system is used to manufacture... Methods for creating 3D products

[0130] As described, the polyamide (A) or composition (C) of the present invention, or any article derived therefrom, can be used as a support material to provide vertical and / or lateral support during 3D printing under the higher operating conditions required by high-temperature part materials (e.g., PEEK requiring room temperatures exceeding 200°C). The 3D printing support material exhibits a high melting temperature (exceeding 250°C), thus imparting heat resistance so as not to soften under high-temperature operating conditions. The support material also has water-absorbing behavior so as to sufficiently expand, disperse, and deform upon exposure to an aqueous medium, or even dissolve in said aqueous medium, thereby enabling easy separation from the target 3D printed part.

[0131] Therefore, another object of the present invention is a method for manufacturing three-dimensional objects using an additive manufacturing system, the method comprising:

[0132] - Provide a support material comprising the polyamide (A) or composition (C) as described above;

[0133] -Provide parts materials;

[0134] - A layer of sacrificial support structure is printed from the provided support material, and layers of the three-dimensional object are printed from the provided part material in coordination with the printed support structure layers, wherein at least a portion of the printed layer of the support structure supports the printed layer of the three-dimensional object; and

[0135] - Remove at least a portion of the sacrificial support structure from the three-dimensional object in order to obtain the three-dimensional object.

[0136] The support material is typically composed of a polymer (A) or a composition (C); the support material is typically supplied in a dry state; for this purpose, the support material is typically dried before being transported to and used in the additive manufacturing system.

[0137] Thus, relative to the total weight of the support material, the support material provided to the additive manufacturing system preferably has a moisture content of less than 0.5% wt, more preferably less than 0.2% wt. A preliminary drying step may be required to achieve this low moisture content by heating the support material at atmospheric temperature (in air or nitrogen) or in a vacuum between 60°C and 200°C for the desired duration.

[0138] The part materials provided in the method of the present invention are typically materials that require a processing temperature of at least 300°C or higher. Part materials that are typically associated with the support material in the method of the present invention, as detailed above, are notably polysulfones, including polyethersulfones and polyphenylene sulfones; polyaryletherketones, including polyetheretherketones and polyetherketoneketones; polyetherimides, polyamideimides, polyphenylene sulfides, polyphenylene oxides, liquid crystal polymers, polycarbonates, aromatic and semi-aromatic polyamides, notably including m-phenylenedimethyldiamine adipate (MXD6), etc.

[0139] Typically, the step of printing layers of a three-dimensional object from the part material is performed by printing the part material in a molten state at a temperature of at least 300°C, preferably at least 350°C.

[0140] According to certain preferred embodiments, the method of the present invention is a method for manufacturing three-dimensional objects using an extrusion-based additive manufacturing system, also known as filament manufacturing technology.

[0141] The support material according to these embodiments is provided in the form of filaments. The filaments may have a cylindrical or substantially cylindrical geometry, or may have a non-cylindrical geometry, such as a ribbon filament geometry; furthermore, the filaments may have a hollow geometry, or may have a core-shell geometry, wherein the support material of the present invention is used to form a core or shell.

[0142] However, the support material according to these embodiments can also be provided in powder form, for example, for feeding via a spiral pump printhead.

[0143] When the method is based on an extrusion-based additive manufacturing system, the step of printing layers of the sacrificial support structure from the provided support material includes:

[0144] a) The support material is fed into the discharge head component, which has a through-hole ending at the discharge tip and a circumferential heater for melting the material in the through-hole;

[0145] b) The support material is compressed in the through-hole by a piston, for example, using an unmelted filament as the piston, while simultaneously melting the support material in the discharge head component to extrude a strip of support material from the discharge tip; and

[0146] c) While discharging the support material onto the receiving platform, ensure relative movement between the discharge tip and the receiving platform in the x and y directions to form the cross-sectional shape of the sacrificial support structure; and

[0147] d) While discharging the support material onto the receiving platform, ensure relative movement of the discharge tip and the receiving platform in the z-direction to form the sacrificial support structure in height.

[0148] According to these embodiments, the step of printing layers of a three-dimensional object from the provided part material in coordination with printing these sacrificial support structures advantageously further includes:

[0149] a') The part material is fed into the discharge head component, which has a through hole ending at the discharge tip and a circumferential heater for melting the material in the through hole;

[0150] b') The part material is compressed in the through-hole by a piston, for example, using an unmelted filament as the piston, while simultaneously melting the part material in the discharge head component to extrude a strip of part material from the discharge tip; and

[0151] c) While discharging the support material onto the receiving platform and the sacrificial support structure, ensure relative movement in the x and y directions between the discharge tip and the receiving platform supporting the sacrificial support structure to form the cross-sectional shape of the three-dimensional object, and

[0152] d) While discharging the part material onto the receiving platform and the sacrificial support structure, ensure relative movement in the z-direction between the discharge tip and the receiving platform to form the three-dimensional object in height.

[0153] The method of the present invention includes step (iv): removing at least a portion of the sacrificial support structure from the component in order to obtain a three-dimensional object.

[0154] This method typically involves exposing the component to an aqueous medium.

[0155] When exposed to the aqueous medium, pure water can be used. However, exposure to an aqueous solution acidified by the addition of one or more acids and possibly supplemented with a polar protic solvent (e.g., ethanol, isopropanol, ethylene glycol) or an electrolyte (e.g., sodium chloride, lithium chloride) can be used. Typically, water is present in the aqueous medium used for such exposure at a concentration of at least 30% wt, preferably at least 50% wt.

[0156] Acetic acid can be advantageously used depending on the one or more acids used in the aqueous medium, although other inorganic or organic acids have been found to be equally effective. The concentration of the one or more acids in the aqueous medium is not critical, and even diluted aqueous solutions containing less than about 10% wt, preferably less than about 8% wt, more preferably less than about 6% wt, such as about 5% wt, have been found to be effective.

[0157] This exposure can be achieved in any way.

[0158] According to some embodiments, step (iv) includes contacting / immersing the component in an aqueous medium. In this case, although higher temperatures (up to about 100°C) can also be used, the temperature of the aqueous medium in which the component is immersed / contacted is typically around room temperature, i.e., a temperature of 20°C to 25°C.

[0159] The duration of exposure to the aqueous medium is not particularly limited, and an exposure time of at least 1 hour may be effective and will be adjusted by those skilled in the art according to the geometry of the sacrificial support structure to be separated and dissolved.

[0160] As a result of step (iv), the sacrificial support structure is removed from the component; the sacrificial support structure can advantageously be separated from the three-dimensional object and removed in its solid form. However, the use of polyamide (A) or composition (C) makes it possible to remove the sacrificial support structure by at least partial dissolution in water.

[0161] Example

[0162] method:

[0163] Thermogravimetric analysis (TGA) was performed under nitrogen according to method ASTM E2550.

[0164] Differential scanning calorimetry (DSC) analysis was performed according to method ASTM D3418 using a heating and cooling rate of 20 °C / min. The glass transition temperature and melting temperature were determined from the results of the second heating.

[0165] Gel permeation chromatography (GPC) was performed using a Waters modular SEC instrument, a Waters Alliance 2695 separation module, a Waters 2487 dual absorption detector, a Waters 2414 refractive index detector, a Waters 515 pump, and Waters Empower Pro gel chromatography software, following internal methods. The instrument was equipped with two PL gel 10 μm MiniMixe B 250 × 4.6 mm columns and a guard column. Samples were dissolved at 5–6 g / L in HFIP containing 0.05 M NaFTA; 15 μl of sample was injected. Elution was performed at 40 °C. Results were obtained using a wide MW internal standard. Calibration is performed at 1000, M w =27943, M n =9340, M w / M n =2.99.

[0166] monomer:

[0167] 1-(2-aminoethyl)piperazine (CAS No. 140-31-8); 1,4-bis-(3-aminopropyl)piperazine (CAS No. 7209-38-3); and 1,4-cyclohexanedicarboxylic acid (CAS No. 1076-97-7) are supplied by Aldrich.

[0168] N-(6-aminohexyl)-N-methyl-1,6-hexanediamine (CAS No. 41318-22-3) T-amine is supplied by Invista.

[0169] Other materials:

[0170] White distilled vinegar from Publix, 5 wt% acetic acid

[0171] Compare with Example 1 (AEP, CHDA)

[0172] 7.60 g (58.2 mmol) of a certain compound was added to a 25 g reactor. The reactor contained 1-(2-aminoethyl)piperazine (AEP), 9.73 g (56.5 mmol) cyclohexanedicarboxylic acid (CHDA), 15.4 mg sodium hypophosphite (0.145 mmol), and 7.33 g deionized water. The system was purged with nitrogen for 5 minutes, and then the reactor was heated to 280 °C and a pressure of 300 psig (20.7 bar). The pressure was maintained at 300 psig for 30 minutes while the temperature was increased to 288 °C. Over 50 minutes, the pressure was slowly released from 300 psig to ambient pressure. The temperature was maintained at 280 °C for 50 minutes until nitrogen was purged through the system and the reactor was shut off for cooling. The product was removed from the reactor as a light amber-colored, transparent resin. This resin had a Mn content of 9.1 kg / mol, a Mw content of 15.9 kg / mol (PDI-1.74), and a glass transition at 166 °C; the melting temperature was not determined, indicating that a substantially amorphous polyamide was obtained.

[0173] Compare the solubility of Example 1

[0174] Add 1.08g of resin and 2.08g of household white vinegar to a small glass vial and shake. The resin will completely dissolve overnight at room temperature, producing a uniform brown, viscous solution.

[0175] Example 2 (mBHT, CHDA)

[0176] 9.81 g (42.1 mmol) of a certain formula was added to a 25 g reactor. The reactor contained N-methyl-bis-hexamethylenetriamine (mBHT), 7.05 g (40.9 mmol) of cyclohexanedicarboxylic acid (CHDA), 20.0 mg of sodium hypophosphite (0.145 mmol), and 6.80 g of deionized water. Nitrogen was purged through the system for 5 minutes, and the reactor was then heated to 280 °C and a pressure of 300 psig (20.7 bar). The pressure was maintained at 300 psig for 30 minutes while the temperature was increased to 288 °C. Over 50 minutes, the pressure was slowly released from 300 psig to ambient pressure. The temperature was maintained at 280 °C for 50 minutes until nitrogen was purged through the system and the reactor was shut off for cooling. The product, appearing as opaque, creamy-colored lumps, was removed from the reactor.

[0177] Solubility of Example 2

[0178] Add 6.17g of resin and 15.0g of household white vinegar to a glass vial and shake. The resin will completely dissolve overnight at room temperature, producing a clear, homogeneous solution.

[0179] Example 3 (BAPP, CHDA)

[0180] 9.29 g (45.9 mmol) of a certain compound was added to a 25 g reactor. The reactor contained 4-bis(3-aminopropyl)piperazine (BAPP), 7.68 g (44.6 mmol) cyclohexanedicarboxylic acid (CHDA), 12.0 mg phosphorous acid (0.145 mmol), and 7.14 g deionized water. Nitrogen gas was purged through the system for 5 minutes, and the reactor was then heated to 275 °C and 320 psig. The pressure was maintained at 320 psig for 40 minutes while the reactor temperature was increased to 285 °C. The pressure was slowly released from the reactor for 45 minutes until ambient pressure was reached. The reactor temperature was maintained at 285 °C for 45 minutes until nitrogen gas was purged through the system and the reactor was shut off for cooling. The product was collected as a homogeneous, opaque, pale yellow mass.

[0181] Solubility of Example 3

[0182] Add 0.4 g of Example 3 resin and 6.4 g of distilled water to a vial. Place the vial on a Burrell wrist shaker and stir overnight. The resin sample decomposes into a turbid dispersion.

[0183] Add 0.46 g of the product from Example 3 and 4.74 g of a 6.5 wt% aqueous solution of citric acid to a vial. Stir the solution overnight to produce a turbid dispersion consisting of small solid precipitates and a suspension.

[0184] Table 1

[0185]

[0186] These examples, in addition to demonstrating good molecular weight and thermal properties, also show easy solubility and dispersion in a mildly acidic solution—household vinegar containing 5 wt% acetic acid. The high Tm2 of Examples 2 and 3 demonstrates that amines (N... N 1 ) and amines (N N 2 The unique structure of this compound is crucial for combining high melting behavior with easy solubility in mild acidic aqueous media. Indeed, the combination of acid (CH2A) with diamine (which, even with the inclusion of a tertiary amine group, does not provide two -(CH2) groups) is essential. n The polyamide of Example 1C (comparative) (-NH2 part) results in an amorphous structure, which is not suitable for withstanding high temperature conditions.

[0187] Data from Examples 2 and 3 demonstrate that the materials of this invention can be used for fused wire printing at high build chamber temperatures (i.e., temperatures ≥200°C). These compositions allow for the use of soluble support materials at high build chamber temperatures that maximize the mechanical strength of the printed parts.

Claims

1. A (co)polyamide comprising repeating units (R) selected from the group consisting of the following: PA ): - Units with the following formula (R) PA 1 ): Where p and q are either the same or different from each other, and are independent integers from 3 to 9; R H It is a monovalent C1-C6 alkyl group; and - Units with the following formula (R) PA 2 The group selected is composed of the following items: - Units with the following formula: , where r and s are either the same or different from each other, and are independent integers from 1 to 3; - Units with the following formula: , where r and s are either the same or different from each other, and are independent integers from 1 to 3; The (co)polyamide is semi-crystalline and has both an amorphous and a crystalline phase, resulting in a detectable melting point, as determined by differential scanning calorimetry according to ASTM D3418. Furthermore, the (co)polyamide contains approximately 100 mol.% repeating units (R). PA Homopolymers, or homopolymers containing at least 95 mol.% repeating units (R... PA The proportion of repeating units in the copolyamide is given relative to the total molar of repeating units in the (co)polyamide, wherein the expression "substantially" means that, in addition to the listed repeating units, end groups, impurities, defects and other dummy units may also be present in the (co)polyamide relative to the total molar of repeating units of less than 1 mol.% 2. The (co)polyamide as described in claim 1, wherein, In unit (R) PA 1 In the expression ), p and q are either the same or different from each other, and are independent integers from 4 to 6.

3. The (co)polyamide as described in claim 1, wherein, In unit (R) PA 1 In ), each of p and q is 6.

4. The (co)polyamide as described in claim 1, wherein, Unit (R) PA 1 It has the following formula: And R BH It is a C1-C3 alkyl group.

5. The (co)polyamide of claim 1, wherein unit (R) PA 2 ) is a unit with the following formula: , where r and s are either the same or different from each other, and are independent integers from 1 to 3.

6. The (co)polyamide of claim 5, wherein unit (R) PA 2 It has the following formula: .

7. The (co)polyamide according to any one of claims 1-6, wherein the (co)polyamide comprises at most 5 mol.% of repeating units different from those having the following formula (F) relative to the total molar percentage of repeating units of the (co)polyamide: (F)， - where E is a variable with the formula (I) N 1 ) or (I N 2 Any one of the groups in ) (I N 1 ) (I N 2 ) Where R alk ° is the unit price C1-C 12 A hydrocarbon group, which may contain one or more heteroatoms; R alk 1 and R alk 2 Each of them, whether identical or different, is a bond or a divalent C1-C bond. 12 A hydrocarbon group, which may contain one or more heteroatoms, provided that R alk 1 and R alk 2 They are not simultaneously bonds, but together with the nitrogen atoms they are attached to form heterocyclic mononuclear or polynuclear groups; and - n1 and n2 are integers, which may be the same as or different from each other; These repeating units differ from those in equation (F) and conform to any of the following: -NO” H -R 1 -C(O)-(II) -NR’” H -R 2 -NR’” H -C(O)-R 3 -C(O)-(III) Where R” H and R'” H They are the same or different from each other and each time they appear, they are H or hydrocarbon groups; and R 1 R 2 R 3 They may be the same or different from each other, are divalent hydrocarbon groups, and can be aliphatic, alicyclic, cycloaliphatic, aromatic, or a combination thereof, wherein R 1 R 2 R 3 It may contain one or more heteroatoms selected from the group consisting of O, N, S, and P.

8. The (co)polyamide according to any one of claims 1-6, having a number-average molecular weight M ranging from 1,000 g / mol to 50,000 g / mol. N The number-average molecular weight was determined by gel permeation chromatography (GPC) following the instructions in ASTM D5296 with reference to substantially monodisperse polystyrene standards.

9. The (co)polyamide according to any one of claims 1-6, having a crystallinity such that its heat of fusion is at least 5 J / g when determined by differential scanning calorimetry according to ASTM D3418.

10. The (co)polyamide of claim 9, having a crystallinity such that its heat of fusion is at least 10 J / g when determined by differential scanning calorimetry according to ASTM D3418.

11. The (co)polyamide of claim 9, having a crystallinity such that its heat of fusion is at least 15 J / g when determined by differential scanning calorimetry according to ASTM D3418.

12. The (co)polyamide according to any one of claims 1-6, having a melting point of at least 250°C, as determined according to ASTM D3418.

13. A method for preparing polyamide (A) as described in any one of claims 1-12, said method comprising thermally polycondensing a monomer mixture of one or more 1,4-cyclohexanedicarboxylic acids [acid (CHDA)] (or a derivative thereof) and a diamine component consisting of one or more diamines having any one of the following formulas (or a derivative thereof): [amine(N] N 1 )] Where R alk ° is a monovalent C1-C6 alkyl group, n1 and n2 are the same or different from each other and are integers from 3 to 9 each time they appear; 1,4-Bis(aminoalkyl)piperazine[amine(N N 2 )], wherein the aminoalkyl group is selected from aminomethyl, aminoethyl, and aminopropyl groups; And may additionally contain at least one mixture selected from the following: - A mixture (M1) comprising at least one diacid [acid (DA)] (or a derivative thereof) and at least one diamine [amine (NN)] (or a derivative thereof), wherein (i) the acid (DA) is not an acid (CHDA) and / or (ii) the amine (NN) is not an amine (N) N 1 It is not an amine (N) N 2 ); - A mixture (M2) containing at least one lactam [lactam (L)]; - A mixture (M3) containing at least one aminocarboxylic acid [amino acid (AN)]; and - The combination is as described above.

14. The method of claim 13, wherein, In monomer mixtures, the molar ratio n 二酸 / n 二胺 It is in the range of 0.8 to 1.

2.

15. The method of claim 14, wherein, In monomer mixtures, the molar ratio n 二酸 / n 二胺 It is in the range between 0.9 and 1.

1.

16. The method of claim 14, wherein, In monomer mixtures, the molar ratio n 二酸 / n 二胺 It is in the range between 0.95 and 1.

05.

17. The method of claim 14, wherein, In monomer mixtures, the molar ratio n 二酸 / n 二胺 It is in the range between 0.98 and 1.

02.

18. A composition (C) comprising at least one (co)polyamide as claimed in any one of claims 1 to 12, and further comprising at least one component selected from the group consisting of: reinforcing agents, toughening agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, nucleating agents, crosslinking agents, and antioxidants.

19. The composition (C) of claim 18, comprising at least one (co)polyamide as described in any one of claims 1 to 12, and further comprising at least one reinforcing filler selected from fibrous fillers.

20. The composition (C) of claim 19, wherein the reinforcing filler is selected from glass fiber and carbon fiber.

21. A molded article made of the composition (C) as described in any one of claims 18-20 or the (co)polyamide as described in any one of claims 1 to 12.

22. A method for manufacturing a three-dimensional object using an additive manufacturing system, the method comprising: - Provide a support material comprising the (co)polyamide as described in any one of claims 1 to 12 or the composition (C) as described in any one of claims 18-20; - Provide parts materials; - A layer of sacrificial support structure is printed from the provided support material, and a layer of the three-dimensional object is printed from the provided part material in coordination with the layer of the printed support structure, wherein at least a portion of the printed layer of the support structure supports the printed layer of the three-dimensional object. as well as - Remove at least a portion of the sacrificial support structure from the three-dimensional object to obtain the three-dimensional object.

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