Polyamide and corresponding polymer compositions, articles, and methods of making and using

Abstract

This specification describes polyamides (PA) incorporating cycloaliphatic monomers containing cyclohexyl groups. Surprisingly, it has been discovered that by incorporating cycloaliphatic monomers containing cyclohexyl groups, the resulting polyamides (PA) have significantly reduced water absorption while maintaining good mechanical properties compared to both similar polyamides that do not contain cycloaliphatic monomers and compared to both PA6,T-based polyamides copolymerized with either or both isophthalic acid and adipic acid.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is This is a national phase entry of International Application No. PCT / EP2020 / 073751, filed on August 25, 2020, This application claims priority to U.S. Provisional Patent Application No. 62 / 892,042, filed August 27, 2019. the The entire contents are incorporated herein by reference for all purposes.

[0002] Revised Polyamide with improved water absorption and good mechanical properties The polyamide A polymer composition comprising ,and Articles Comprising Such Polymers and Polymer Compositions is offered in the same way . [Background technology]

[0003] Polyamides such as PA6,T are generally polymerized with comonomers such as isophthalic acid or adipic acid. Being Such polyamides have the outstanding mechanical performance and chemical resistance of PA6,T, but can be processed at lower temperatures due to the presence of the comonomer. However, the incorporation of isophthalic acid or adipic acid into PA6 results in polyamides with increased moisture absorption, reducing the dimensional stability of articles formed from such polymers. Thus, there is a need for polyamides that have the excellent mechanical performance and chemical resistance of PA6,T-based copolyamides, but with reduced moisture absorption. Summary of the Invention

[0004] In one embodiment, Polyamide (PA) is provided. Polyamide (PA) 55 mol% to 75 mol% of C4 to C8 aliphatic diamines, 25 mol% to 45 mol% of C9 to C 12 A diamine component (A) containing an aliphatic diamine and 0 mol % to 10 mol % of an alicyclic diamine containing a cyclohexyl group, the mol % being based on the total number of moles of diamine in the diamine component (A), and a diamine component (A) containing 90 mol % to 100 mol % of terephthalic acid, 0 mol % to 10 mol % of C6 to C 18Aliphatic dicarboxylic acids or C8-C different from terephthalic acid 18 A dicarboxylic acid component (B) containing an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid containing 0 mol % to 10 mol % of a cyclohexyl group, the mol % being based on the total number of moles of dicarboxylic acids in the dicarboxylic acid component (B), and a C8 to C6 dicarboxylic acid containing 0 mol % to 9 mol % of a cyclohexyl group. 10 and an alicyclic amino acid, the mole percent of which is based on the total moles of dicarboxylic acid in the dicarboxylic acid component (B), and wherein one of the alicyclic diamine, alicyclic dicarboxylic acid, and alicyclic amino acid is formed from the polycondensation of a reaction mixture (RM) having a concentration of greater than 0.5 mole percent. do. In some embodiments, only one of the alicyclic diamine, alicyclic dicarboxylic acid, and alicyclic amino acid is , in the reaction mixture In some embodiments, the reaction mixture (RM) has a concentration of more than 0.5 mol %, and the reaction mixture (RM) does not contain two other alicyclic monomers containing cyclohexyl groups. Additionally or alternatively, in some embodiments, the reaction mixture (RM) has a concentration of more than 0.5 mol %, and the reaction mixture (RM) does not contain two other alicyclic monomers containing cyclohexyl groups. 18 Aliphatic Dicarboxylic Acids and / or C8-C different from terephthalic acid 18 Contains no aromatic dicarboxylic acids.

[0005] In another embodiment, A polymer composition (PC) is provided. Polyamide (PA) and reinforcing agents, toughening agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants ( Halogen-free flame retardants etc.) , nucleating agents and antioxidants and at least one component selected from the group consisting of , preferably The polymer composition (PC) is At least halogen-free flame retardant Agent In some embodiments, the polymer composition (PC) comprises 10% to 60% by weight of glass fibers, based on the total weight of the polymer composition (PC). In some embodiments, the polymer composition (PC) comprises 30% to 60% by weight of glass fibers, based on the total weight of the polymer composition (PC). 99.95 Contains wt.% polyamide (PA). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] Described herein are polyamides (PA) incorporating cycloaliphatic monomers containing cyclohexyl groups. Surprisingly, by incorporating cycloaliphatic monomers containing cyclohexyl groups, the resulting polyamides (PA) are similar to both analogous polyamides that do not contain cycloaliphatic monomers. D, and copolymerized with either or both of isophthalic acid and adipic acid was done It was found that, compared to PA6,T-based polyamides, they have significantly reduced water absorption while maintaining good mechanical properties. Moreover, unexpectedly, at relatively low concentrations of cycloaliphatic monomers containing cyclohexyl groups, polyamides (PA) Contains a cyclohexyl group It has been discovered that, compared to similar polyamides that do not contain alicyclic monomers, they have significantly increased glass transition temperatures ("Tg") while maintaining high melting temperatures ("Tm") and crystallization temperatures ("Tc").

[0007] Polyamide (PA) is a compound that is a mixture of alicyclic diamines containing cyclohexyl groups, alicyclic dicarboxylic acids containing cyclohexyl groups, and C8-C containing cyclohexyl group 10 Of course, in some embodiments, the reaction mixture (RM) may include two or more different cycloaliphatic monomers containing a cyclohexyl group, where each of the cycloaliphatic amino acids is selected from the group consisting of cycloaliphatic amino acids. alicyclic The monomers include an alicyclic diamine containing a cyclohexyl group, an alicyclic dicarboxylic acid containing a cyclohexyl group, and C8-C containing cyclohexyl group 10 alicyclic amino acids.

[0008] Unless specifically limited otherwise, the terms "alkyl" and derivative terms such as "alkoxy", "acyl" and "alkylthio", as used herein, include within their scope linear, branched and cyclic moieties. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, and cyclopropyl. Unless specifically stated otherwise, each alkyl and aryl group may be unsubstituted or substituted with halogen, hydroxy, sulfo, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C6 alkylthio, C1 ... 15 Aryloxy or C6~C 15 It may be substituted with one or more substituents selected from, but not limited to, aryl, provided that the substituents are sterically compatible and chemical bonding and strain energy rules are satisfied. The term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine, with fluorine being preferred.

[0009] The term "aryl" refers to a phenyl, indanyl, or naphthyl group. An aryl group may contain one or more alkyl groups, in which case it is referred to as "alkylaryl." Say Sometimes ; For example, it may be composed of an aromatic group and two C1-C6 groups (e.g., methyl or ethyl). The aryl group may also contain one or more heteroatoms, such as N, O, or S, in which case it is referred to as a "heteroaryl" group. Say Sometimes ; These heteroaromatic rings may be fused with other aromatic systems. Such heteroaromatic rings include, but are not limited to, furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl, and triazinyl ring structures. The aryl or heteroaryl substituents may be unsubstituted or may be selected from halogen, hydroxy, C1-C6 alkoxy, sulfo, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C6 alkylthio, C1-C6 aryl ... 15 Aryloxy or C6~C 15It may be substituted with one or more substituents selected from, but not limited to, aryl, provided that the substituents are sterically compatible and chemical bonding and strain energy rules are satisfied.

[0010] Reaction mixture The polyamide (PA) is formed by polycondensation of a reaction mixture (RM) containing a diamine component (A), a dicarboxylic acid component (B), and an amino acid component (C). The diamine component (A) is a mixture of 55 mol % to 75 mol % of a C4 to C8 aliphatic diamines, 25 mol % to 45 mol % of a C9 to C 12 The diamine component (A) contains an aliphatic diamine and 0 mol % to 10 mol % of an alicyclic diamine containing a cyclohexyl group, where mol % is based on the total number of moles of diamine in the diamine component (A). The dicarboxylic acid component (B) contains 90 mol % to 100 mol % of terephthalic acid, 0 mol % to 10 mol % of C6 to C 18 Aliphatic dicarboxylic acids or C8-C different from terephthalic acid 18 The amino acid component (C) is a C8-C alicyclic dicarboxylic acid containing 0 mol % to 9 mol % of a cyclohexyl group, and the mol % is based on the total number of moles of dicarboxylic acids in the dicarboxylic acid component (B). 10 and alicyclic amino acids, where the mole percentages are based on the total moles of dicarboxylic acid component (B). For clarity, C4-C8 aliphatic diamines and C9-C 12 The aliphatic diamine can be a linear or branched aliphatic diamine. Preferably, C4-C8 aliphatic diamines and C9-C 12 Both aliphatic diamines are linear aliphatic diamines. Similarly, C6-C 18 The aliphatic dicarboxylic acid can be a linear or branched aliphatic dicarboxylic acid. , J Amines, dicarboxylic acids, and Optional Amino Acids eachThe concentrations are selected such that [-NH2] / [-COOH] is between 0.9 and 1.1, preferably between 0.95 and 1.05, where [-NH2] and [-COOH] are the moles of -NH2 and -COOH groups, respectively, in the reaction mixture (RM).

[0011] For ease of reference, as used hereinafter, the concentration of a diamine refers to its concentration relative to the total moles of diamine in the diamine component (A), unless otherwise specified. Similarly, as used hereinafter, the concentration of a dicarboxylic acid refers to its concentration relative to the total moles of dicarboxylic acid in the dicarboxylic acid component (B). In addition, as used hereinafter, the concentration of an amino acid refers to its concentration relative to the total moles of dicarboxylic acid in the dicarboxylic acid component (B). Dicarboxylic acid As used herein, "free" with respect to a monomer in a reaction mixture (RM) means that the indicated monomer is: Reaction mixture 0.5 in Mole %, preferably less than 0.1 Mole %. For example, if the reaction mixture (RM) does not contain a cycloaliphatic diamine containing a cyclohexyl group, Reaction mixture (RM) Its concentration in is 0.5 Mole %, preferably less than 0.1 Mole % or less.

[0012] Importantly, as noted above, cycloaliphatic diamines containing cyclohexyl groups, cycloaliphatic dicarboxylic acids containing cyclohexyl groups, and C-C alkyl esters containing cyclohexyl groups are also included. 10 One of the alicyclic amino acids is In reaction mixture (RM) Of course, in some embodiments, any two or all of the cycloaliphatic monomers containing a cyclohexyl group have a concentration of greater than 0.5 mole percent. In reaction mixture (RM) In some embodiments, only one of the three cycloaliphatic monomers containing a cyclohexyl group has a concentration of more than 0.5 mol %, and the reaction mixture (RM) contains the other two cycloaliphatic monomers containing a cyclohexyl group. Does not include .

[0013] The diamine component (A) is All of Similarly, the dicarboxylic acid component (B) contains all the diamines in the reaction mixture (RM). All of Contains all dicarboxylic acids and amino acid components minutes , in reaction mixture (RM) No.A Contains all amino acids.

[0014] In some embodiments, the diamine component (A) is 0.5 mol %~ In one such embodiment, the reaction mixture (RM) comprises 10 mol %, preferably 1 mol % to 10 mol % of an alicyclic diamine containing a cyclohexyl group. 18 Aliphatic dicarboxylic acids 、 C8-C different from terephthalic acid 18 Aromatic dicarboxylic acids, alicyclic dicarboxylic acids containing a cyclohexyl group, and / or C8-C containing cyclohexyl group 10 Contains no alicyclic amino acids .stomach Some Such In an embodiment, reaction mixture (RM) does not include additional diamines, additional dicarboxylic acids, and additional amino acids. For clarity, additional monomers refers to monomers that were not explicitly listed in reaction mixture (RM) as defined above.

[0015] In some embodiments, the dicarboxylic acid component (B) is 0.5 mol %~ In one such embodiment, the reaction mixture (RM) comprises 10 mol %, preferably 1 mol % to 10 mol % of an alicyclic dicarboxylic acid containing a cyclohexyl group. In one such embodiment, the reaction mixture (RM) comprises an alicyclic diamine containing a cyclohexyl group, a C6-C 18 Aliphatic dicarboxylic acids 、 C8-C different from terephthalic acid 18 Aromatic dicarboxylic acids, and / or C8-C containing cyclohexyl group 10 Contains no alicyclic amino acids .stomach Some Such In an embodiment, the reaction mixture (RM) other than those explicitly listed in relation to the reaction mixture (RM) as defined above., additional diamines, additional dicarboxylic acids and additional amino acids.

[0016] In some embodiments, the amino acid component (C) is 0.5 mol %~ C8-C containing 10 mol %, preferably 1 mol % to 10 mol % of cyclohexyl groups 10 In one such embodiment, the reaction mixture (RM) comprises a cycloaliphatic diamine containing a cyclohexyl group, a C6-C 18 Aliphatic dicarboxylic acids 、 C8-C different from terephthalic acid 18 Aromatic dicarboxylic acids, and / or Does not contain cycloaliphatic dicarboxylic acids containing cyclohexyl groups .stomach Some Such In an embodiment, the reaction mixture (RM) comprises Explicitly stated in relation to the reaction mixture (RM) as defined above It does not contain additional diamines, additional dicarboxylic acids, or additional amino acids.

[0017] Diamine component (A) The diamine component (A) is composed of 55 mol % to 75 mol % of a C4 to C8 aliphatic diamines and 25 mol % to 45 mol % of a C9 to C 12 Includes aliphatic diamines and alicyclic diamines containing 0 mol % to 10 mol % of a cyclohexyl group.

[0018] In some embodiments, C4-C8 aliphatic diamines and C9-C 12 The diamines are represented by the following formula: (1) and (2) : H2N-R1-NH2, (1) and H2N-R2-NH2, (2) (Wherein, R1 is a C4 to C8 aliphatic alkyl group, preferably a C6 aliphatic alkyl group, and R2 is a C9 to C 12 Aliphatic alkyl groups, preferably C 10 aliphatic alkyl group) In some embodiments, the C4-C8 aliphatic diamine is selected from the group consisting of 1,4-diaminobutane ("putrescine"), 1,5-diaminopentane ("cadaverine"), 2-methyl-1,5-diaminopentane, hexamethylenediamine ("HMDA"), 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 1,7-diaminoheptane, and 1,8-diaminooctane. 12 The aliphatic diamine is selected from the group consisting of 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine, 2-ethyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. Preferably, the C4-C8 aliphatic diamine is HMDA. and / or is C9~C 12 The aliphatic diamine is 1,10-diaminodecane. Most preferably, the C4-C8 aliphatic diamine is HMDA and the C9-C 12 The aliphatic diamine is 1,10 diaminodecane.

[0019] In some embodiments, the cycloaliphatic diamine containing a cyclohexyl group has the formula: (3) and (4) : [ka] (In the formula, R3 and R4 are a bond and C1 to C 10 alkyl groups, R' is independently selected at each occurrence from the group consisting of alkyl, aryl, alkali or alkaline earth metal sulfonates, alkyl sulfonates, and quaternary ammonium, and each i is an integer independently selected from 0 to 10. In formula (3), preferably, the -R3-NH2 and -R4-NH2 groups are disposed relative to the meta (1,3-) or para (1,4-) positions, most preferably the meta positions. In some embodiments, the cycloaliphatic diamine containing a cyclohexyl group is selected from the group consisting of isophorone diamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis-p-aminocyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), 1,4-bis(aminomethyl)cyclohexane ("1,4-BAC"), bis(4-amino-3-methylcyclohexyl)methane, and bis(4-aminocyclohexyl)methane. Preferably, the cycloaliphatic diamine containing a cyclohexyl group is 1,3-BAC or 1,4-BAC, most preferably 1,3-BAC. Of course, cycloaliphatic diamines containing cyclohexyl groups according to formula (3) (e.g., 1,3-BAC and 1,4-BAC) can be in the cis or trans conformation, and thus the diamine component (A) can contain only the cis isomer, only the trans isomer, or a mixture of cis and trans isomers.

[0020] In some embodiments, the concentration of the C4-C8 aliphatic diamine is 60 mol % to 70 mol %. 12 The concentration of the aliphatic diamine is 30 mol% to 45 mol%, preferably 25 mol% to 38 mol%, more preferably 30 mol% to 38 mol%. In some embodiments, the concentration of the cycloaliphatic diamine containing a cyclohexyl group is 1 mol% to 10 mol%, preferably 3 mol% to 10 mol%. In some embodiments, the reaction mixture (RM) does not contain an cycloaliphatic diamine containing a cyclohexyl group.

[0021] In some embodiments, C4-C8 aliphatic diamines, C9-C 12The total concentration of the aliphatic diamine and the cycloaliphatic diamine containing a cyclohexyl group is at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, at least 99.5 mol%, or at least 99.9 mol%. In some embodiments, the diamine components (A) are different from each other and are C4-C8 aliphatic diamines, C9-C 12 In some such embodiments that include additional diamines, the diamines may include C4-C8 aliphatic diamines, C9-C 12 Aliphatic Diamines , S The total concentration of cycloaliphatic diamines containing cyclohexyl groups are all within the corresponding ranges given above. In other such embodiments including additional diamines, the concentration of each additional diamine is C4-C8 aliphatic diamine, C9-C 12 The ranges given above for aliphatic diamines and cycloaliphatic diamines containing cyclohexyl groups are different.

[0022] Dicarboxylic acid component (B) The dicarboxylic acid component (B) is 90 mol % to 100 mol % of terephthalic acid, 0 mol % to 10 mol % of C6 to C 18 Aliphatic dicarboxylic acids or C8-C different from terephthalic acid 18 These include aromatic dicarboxylic acids and alicyclic dicarboxylic acids containing 0 mol % to 10 mol % of a cyclohexyl group.

[0023] In some embodiments, C 18Aliphatic dicarboxylic acids include 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], pimelic acid [HOOC-(CH2)5-COOH], suberic acid [HOOC-(CH2)6-COOH], azelaic acid [HOOC-(CH2)7-COOH], sebacic acid [HOOC-(CH2)8-COOH], undecanedioic acid [HOOC-(CH2)9-COOH], dodecanedioic acid [HOOC-(CH2) 10 -COOH], tridecanedioic acid [HOOC-(CH2) 11 -COOH], tetradecanedioic acid [HOOC-(CH2) 12 -COOH], pentadecanedioic acid [HOOC-(CH2) 13 -COOH], hexadecanedioic acid [HOOC-(CH2) 14 -COOH], and octadecanedioic acid [HOOC-(CH2) 16 —COOH]. Preferably, C6 to C 18 The aliphatic dicarboxylic acid is adipic acid or sebacic acid, most preferably adipic acid.

[0024] In some embodiments, a C8-C 18The aromatic dicarboxylic acid is selected from the group consisting of phthalic acid, naphthalenedicarboxylic acid (e.g., naphthalene-2,6-dicarboxylic acid), 4,4'-bibenzoic acid, 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)ketone, 4,4'-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)ketone, bis(3-carboxyphenoxy)benzene, such as isophthalic acid ("IA"), and excluding terephthalic acid ("TA"). Preferably, the aromatic dicarboxylic acid is selected from the group consisting of C8 to C6 18 The aromatic dicarboxylic acid is naphthalenedicarboxylic acid or 4,4'-bibenzoic acid.

[0025] In some embodiments, the cycloaliphatic dicarboxylic acid containing a cyclohexyl group has the following formula: [ka] wherein R″ is independently selected at each occurrence from the group consisting of alkyl, aryl, alkali or alkaline earth metal sulfonate, alkylsulfonate, and quaternary ammonium, and j is an integer from 0 to 10. In formula (5), the -C-COOH group is preferably disposed relative to the meta (1,3-) or para (1,4-) positions, most preferably the para position. In some embodiments, the cycloaliphatic carboxylic acid containing a cyclohexyl group is cyclohexanedicarboxylic acid ("CHDA"), preferably 1,3-CHDA or 1,4-CHDA, most preferably 1,4-CHDA.

[0026] In some embodiments, the concentration of terephthalic acid is 92 mol % to 100 mol %, preferably 93 mol % to 100 mol %. 18Aliphatic dicarboxylic acids or C8-C different from terephthalic acid 18 The concentration of the aromatic dicarboxylic acid is 0 mol % to 0.5 mol %, preferably 0 mol % to 0.1 mol %. In some embodiments, the concentration of the cycloaliphatic dicarboxylic acid containing a cyclohexyl group is 3 mol % to 9 mol %. In some embodiments, the dicarboxylic acid component (B) is 、C 6~C 18 fat Tribe C8-C different from carboxylic acid or terephthalic acid 18 Aromatic dicarboxylic acids , and An alicyclic dicarboxylic acid containing a cyclohexyl group. , 2 or Three Does not include.

[0027] In some embodiments, terephthalic acid, C6-C 18 Aliphatic dicarboxylic acids 、 C8-C different from terephthalic acid 18 The total concentration of the aromatic dicarboxylic acid and the cycloaliphatic dicarboxylic acid containing a cyclohexyl group is at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, at least 99.5 mol%, or at least 99.9 mol%. In some embodiments, the dicarboxylic acid components (B) are each independently selected from each other and from terephthalic acid, C6-C 18 Aliphatic dicarboxylic acids 、 C8-C different from terephthalic acid 18 Additional dicarboxylic acids different from the aromatic dicarboxylic acids and the cycloaliphatic dicarboxylic acids containing cyclohexyl groups can be included. In some such embodiments including additional dicarboxylic acids, C6-C 18 Aliphatic dicarboxylic acids 、 C8-C different from terephthalic acid 18 Aromatic dicarboxylic acids Acid and cyclohexyl groups Fat Cyclic dicarboxylic acids Total concentration of In other such embodiments that include additional dicarboxylic acids, the concentration of each additional dicarboxylic acid is C6 to C 18 Aliphatic dicarboxylic acids、 C8-C different from terephthalic acid 18 The ranges given above for aromatic dicarboxylic acids and alicyclic dicarboxylic acids containing cyclohexyl groups are different.

[0028] Amino acid composition (C) The amino acid component (C) contains C8-C cyclohexyl groups at 0 mol % to 9 mol %. 10 Contains alicyclic amino acids where mole percent is based on the total moles of dicarboxylic acid in dicarboxylic acid component (B). .

[0029] In some embodiments, a C8-C 10 Alicyclic amino acids have the formula: [ka] (wherein R5 is a C1 to C3 alkyl group, preferably a C1 alkyl group). Preferably, the C8 to C 10 The alicyclic amino acid is 4-aminomethylcyclohexane carboxylic acid ("4-AMCC"). Of course, the alicyclic amino acid according to formula (6) can be in the cis or trans conformation. Thus, the amino acid component (C) can include only the cis isomer, only the trans isomer, or a mixture of cis and trans isomers.

[0030] In some embodiments, a C8-C 10 The concentration of the alicyclic amino acid is 1 mol% to 9 mol%, preferably 3 mol% to 9 mol%. where mole % is based on the total moles of dicarboxylic acid in dicarboxylic acid component (B). In some embodiments, the reaction mixture (RM) comprises a C8-C cyclohexyl group-containing 10 In some such embodiments, the amino acid component (C) is a C-C cyclic amino acid that contains a cyclohexyl group. 10 It may or may not contain additional amino acids different from the alicyclic amino acids, hi some embodiments, the reaction mixture (RM) does not contain any amino acids.

[0031] In some embodiments, a C8-C 10 The total concentration of alicyclic amino acids is at least 90 mol%, at least 95 mol%, at least 98 mol%, at least 99 mol%, at least 99.5 mol%, or at least 99.9 mol% relative to the total amount of amino acids in amino acid component (C). In some embodiments, amino acid component (C) is a mixture of each of the C8 to C6 alicyclic amino acids, each of which is a C6 to C8 alicyclic amino acid. 10 In some such embodiments that include additional amino acids, the amino acids may be C8-C cyclohexyl-containing amino acids. 10 Alicyclic Amino Acids and additional amino acids In other such embodiments that include additional amino acids, the total concentration of each additional No.A The concentration of amino acids is C8-C 10 The ranges given above for alicyclic amino acids are different.

[0032] Polyamide (PA) synthesis The polyamides (PA) described herein can be prepared by any conventional method adapted for the synthesis of polyamides and polyphthalamides. Preferably, the polyamides (PA) are melted at a temperature of at least Tm+10° C. (Tm being the melting temperature of the polyamides (PA)) in the presence of less than 60% by weight, preferentially less than 50% by weight of water. Reaction mixture (RM) where the weight percent is based on the total weight of the reaction mixture (RM).

[0033] The polyamides (PA) described herein can be prepared, for example, by thermal polycondensation (also referred to as polycondensation or condensation) of aqueous solutions of monomers and comonomers. In one embodiment, the polyamides (PA) are formed by reacting diamines, dicarboxylic acids, and amino acids in a reaction mixture (RM). In some embodiments, the total number of moles of diamines in the diamine component (A) is substantially equimolar to the total number of moles of dicarboxylic acids in the dicarboxylic acid component (B). As used herein, substantially equimolar means a value that is ±15% of the indicated number of moles. For example, in the context of the concentration of diamines and dicarboxylic acids in the respective diamine component (A) and dicarboxylic acid component (B) of the reaction mixture (RM), the total number of moles of diamines in the diamine component (A) is ±15% of the total number of moles of dicarboxylic acids in the dicarboxylic acid component (B). Importantly, as mentioned above, in the reaction mixture (RM), each Diamines, dicarboxylic acids and Optional amino acid Concentration The degree of oxidation is selected so that [-NH2] / [-COOH] is 0.9 to 1.1, preferably 0.95 to 1.05. , where [-NH 2 ] and [-COOH] are the -NH 2 and the total number of moles of -COOH groups. Polyamides (PA) are monofunctional molecules that can react with amine or carboxylic acid moieties and control the molecular weight of the polyamides (PA). R, A chain limiting agent may be included. For example, the chain limiting agent may be acetic acid, propionic acid, benzoic acid and / or benzylamine.

[0034] Catalysts can also be used. Examples of catalysts are phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites such as sodium hypophosphite, and phenylphosphinic acid. Stabilizers, such as phosphites, can also be used.

[0035] Polyamide (PA) Polyamide (PA) is a polymer consisting of three repeating units (R PA1 )~(R PA3 Of course, polyamide (PA) contains the repeating unit (R PA1 )~(R PA3) may have additional repeat units different from

[0036] In some embodiments, the repeating unit (R PA1 ) and (R PA2 ) are expressed by the following formulas, (7) and (8) : [ka] and the repeating unit R PA3 is expressed as follows: (9) or (10) : [ka] (In the formula, R1, R2, and R5 are defined above, and n1 to n3 each represent a repeating unit (R PA1 )~(R PA3 ) mole percent, and T is represented by the formula (11) or (12) : [ka] It is represented by one of where R, R, R' and i are defined above, and "*" represents the formula ( 9 ) to one of the two visible nitrogen atoms in Preferably, T is represented by the formula ( 11 ), preferably where the -R4- group is in the meta (1,3-) position relative to the -R3- group. Additionally or alternatively, in some embodiments, each i is zero. In one embodiment, the repeating unit (R PA1 ) and (R PA2 )teeth each , HMDA and 1,10-diaminodecane are formed by polycondensation with terephthalic acid. Fruit In an embodiment, the repeating unit (R PA3 In another such embodiment, the repeat unit (R PA3 ) is formed from the polycondensation of 4-AMCC. In one embodiment , n1+n2+n3 teeth, At least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol%. As used herein, the concentration of a repeat unit refers to the concentration relative to the total number of repeat units in the polyamide (PA), unless otherwise specified. For example, the repeat units (R PA1 )~(R PA3 ) n1+n2+n3≦100 mol %.

[0037] In some embodiments, the polyamide (PA) comprises four repeat units: the repeat unit (R PA1 ) and (R PA2 ), and, respectively, The following equations (13) and (14) : [ka] (wherein R1, R2, R'', and j are defined above; And in the formula, n 1、 n 2、 n 4 and n 5 are the repeating units (R PA1 )、(R PA2 )、(R PA4 ) and (R PA5 ) is the mole percent of (n 1 +n 2 +n 4 +n 5 ≦100% by mole ) Repeating units represented by (R PA4 ) and (R PA5 ) Preferably, the formula ( 13 ) and ( 14 ) in each of the cyclohexyl rings Above obvious The -COO- group is a para(1, 4) are positioned relative to the On top of that Or alternatively, in some embodiments, j is zero. In one embodiment, the repeat unit (R PA1) and (R PA2 )teeth, each, It is formed by polycondensation of HMDA and 1,10-diaminodecane with terephthalic acid, and has the repeating unit (R PA4 ) and (R PA5 ) are, respectively, It is formed from the polycondensation of HMDA and 1,10-diaminodecane with 1,4-CHDA. In some embodiments, n 1 +n 2 +n 4 +n 5 teeth , at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol%.

[0038] In some embodiments, the polyamide (PA) has a molecular weight of 1,000 g / mol to 40,000 g / mol, 2,000 g / mol to 35,000 g / mol, 4,000 g / mol to 5,000 g / mol, 5,000 g / mol to 6,000 g / mol, 6,000 g / mol to 8,000 g / mol, 8,000 g / mol to 10,000 g / mol, 9,000 g / mol to 12,000 g / mol, 10,000 g / mol to 15,000 g / mol, 10,000 g / mol to 20,000 g / mol, 10,000 g / mol to 25,000 g / mol, 10,000 g / mol to 35,000 g / mol, 10,000 g 0 g / mole The number average molecular weight Mn can be measured by gel permeation chromatography (GPC) using ASTM D5296 with polystyrene standards.

[0039] Polyamides (PA) are semi-crystalline. As used herein, semi-crystalline polyamides have a heat of fusion ("ΔH") of at least 5 Joules per gram (J / g) at a heating rate of 20° C. / min. f "). Similarly, as used herein, amorphous polyamides include those having a ΔH of less than 5 J / g at a heating rate of 20 C / min. f Includes ΔH f can be measured according to ASTM D3418. In some embodiments, ΔH f is at least 20 J / g, at least 30 J / g, or at least 40 J / g.

[0040] In some embodiments, the polyamide (PA) has a Tg of at least 100° C., at least 110° C., or at least 115° C. Additionally or alternatively, in some embodiments, the polyamide (PA) has a Tg of 200° C. or less, 180° C. or less, 160° C. or less, 150° C. or less, 140° C. or less, or 135° C. or less. In some embodiments, the polyamide (PA) has a Tg of 100° C. to 150° C., 110° C. to 140° C., or 115° C. to 135° C. In some embodiments, the polyamide (PA) has a Tg of 100° C. to 200° C., 110° C. to 180° C., or 115° C. to 160° C. In some embodiments, the polyamide (PA) has a Tg of at least 290° C., at least 300° C., or at least 310° C. Tm Additionally or alternatively, in some embodiments, the polyamide (PA) has a Tm of 360° C. or less, 350° C. or less, or 340° C. or less, and in some embodiments, the polyamide (PA) has a Tm of 290° C. to 360° C., 300° C. to 350° C., or 310° C. to 340° C. Tg and Tm can be measured according to ASTM D3418.

[0041] Polymer Composition (PC) The polymer composition (PC) comprises a polyamide (PA). The polyamide (PA) may be present in the polymer composition (PC) in a total amount of more than 30 wt%, more than 35 wt%, more than 40 wt%, or more than 45 wt%, based on the total weight of the polymer composition (PC). The polyamide (PA) may be present in the composition (PC) in a total amount of less than 99.95 wt%, less than 99 wt%, less than 95 wt%, less than 90 wt%, less than 80 wt%, less than 70 wt%, or less than 60 wt%, based on the total weight of the polymer composition (PC). The polyamide (PA) may be, for example, less than 99.95 wt%, less than 99 wt%, less than 95 wt%, less than 90 wt%, less than 80 wt%, less than 70 wt%, or less than 60 wt%, based on the total weight of the polymer composition (PC). 30~70% by weight, 35~60% by weight, or It may be present in the polymer composition (PC) in an amount ranging from 40 to 55% by weight.

[0042] The polymer composition (PC) may also include 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 (including halogen-free flame retardants), nucleating agents, and antioxidants. Preferably, the polymer composition (PC) includes a halogen-free flame retardant, a reinforcing agent (e.g., glass fiber), or both.

[0043] Fibrous or particulate ,A wide selection of reinforcers, Polymer Composition (PC) can be added to Fiber A fiber reinforcing filler is herein considered to be a material having a length, width and thickness, the average length being significantly greater than both the width and thickness. Fiber Reinforcing Filler has an aspect ratio, defined as the average ratio between the length and the maximum width and thickness, of at least 5, at least 10, at least 20, or at least 50. In some embodiments, the reinforcing fibers (e.g., glass or carbon fibers) have an average length of 3 mm to 50 mm. In some such embodiments, the reinforcing fibers have an average length of 3 mm to 10 mm, 3 mm to 8 mm, 3 mm to 6 mm, or 3 mm to 5 mm. In alternative embodiments, the reinforcing fibers have an average length of 10 mm to 50 mm, 10 mm to 45 mm, 10 mm to 35 mm, 10 mm to 30 mm, 10 mm to 25 mm, or 15 mm to 25 mm. The average length of the reinforcing fibers can be considered as the average length of the reinforcing fibers before incorporation into the polymer composition (PC) or after incorporation into the polymer composition (PC). After being incorporated into It can be considered as the average length of the reinforcing fibers.

[0044] The reinforcing fillers may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibres, carbon fibres, synthetic polymer fibres, aramid fibres, aluminium fibres, titanium fibres, magnesium fibres, boron carbide fibres, rock wool fibres, steel fibres and wollastonite.

[0045] Among fibrous fillers, glass fibers are preferred, including chopped strand A-, E-, C-, D-, S- and R-glass fibers, as described in Additives for Plastics Handbook, 2nd edition, John Murphy, Chapter 5.2.3, pages 43-48. Preferably, the filler is selected from fibrous fillers. More preferably, the filler is a reinforcing fiber that can withstand high temperature applications.

[0046] The reinforcing agents may be present in the polymer composition (PC) in a total amount of more than 15 wt%, more than 20 wt%, more than 25 wt%, or more than 30 wt%, based on the total weight of the polymer composition (PC). The reinforcing agents may be present in the polymer composition (PC) in a total amount of 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 (PC). The reinforcing fillers may, for example, be present in the polymer composition (PC) in an amount ranging from 20 to 60 wt%, for example from 30 to 50 wt%, based on the total weight of the polymer composition (PC).

[0047] The polymer composition (PC) may also contain a toughening agent. The toughening agent generally has a Tg below room temperature, below 0° C. or even below −25° C. Low Tg Poly The toughening agent is typically elastomeric at room temperature. . strengthThe functionalizing agent can be a functionalized polymer backbone. The polymer backbone of the toughening agent can be selected from elastomeric 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 a mixture of one or more of the above.

[0048] When the toughening agent is functionalized, the backbone functionalization results from the copolymerization of monomers containing functional groups. mosquito or further sensualization The functionalized toughening agent may result from grafting of the polymer backbone with a component. Specific examples of functionalized toughening agents include, but are not limited to, terpolymers of ethylene, acrylic esters and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylate, copolymers of ethylene, butyl ester acrylate and glycidyl methacrylate, ethylene-maleic anhydride copolymers, EPR grafted with maleic anhydride, styrene 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.

[0049] The toughening agents may be present in the polymer composition (PC) in a total amount of more than 1 wt%, more than 2 wt%, or more than 3 wt%, based on the total weight of the polymer composition (PC). The toughening agents may be present in the polymer composition (PC) in a total amount of 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 (PC).

[0050] The polymer composition (PC) may also contain other conventional additives commonly used in the art, such as plasticizers, colorants, pigments (e.g., black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g., linear low density polyethylene, calcium or magnesium stearate, or sodium montanate), heat stabilizers, light stabilizers, flame retardants, nucleating agents, and antioxidants.

[0051] The polymer composition (PC) may also contain one or more other polymers, preferably Hapo These may include polyamides different from the polyamides (PA), including, inter alia, semicrystalline 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.

[0052] Preparation of polymer composition (PC) above A method for producing a polymer composition (PC) as detailed in is also provided , the method teeth The process includes melt blending polyamide (PA) with certain ingredients, such as fillers, reinforcing agents, stabilizers, and any other optional additives. nothing.

[0053] PAny 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 or twin screw extruder, a stirrer, a single or twin screw kneader, or a Banbury mixer, and the addition step can be simultaneous addition of all components or batchwise stepwise addition. When the polymeric and non-polymeric components are added gradually batchwise, a portion of the polymeric and / or non-polymeric components is added first and then melt mixed with the remaining polymeric and non-polymeric components added thereafter until a well-mixed composition is obtained. When the reinforcing agent is in a long physical form, the reinforcing agent can be added in a short time. Condition ( e.g. long glass fibers) In the case where the stretching is performed in the preparation of the polymer composition (PC), It can be used.

[0054] Articles and uses The polyamide (PA) and polymer composition (PC) may be desirably incorporated into an article.

[0055] Such articles are: They can be used in portable electronics, LED packaging, oil and gas components, food contact components (including, but not limited to, food films and casings), electrical and electronic components (including, but not limited to, power supply components for computing, data systems and office equipment, and surface mount technology compatible connectors and contacts), medical equipment components, construction components (including, but not limited to, pipes, connectors, manifolds and valves for cooling and heating systems, boiler and meter components, gas system pipes and accessories, and electrical protection devices for mini circuit breakers, contactors, switches and sockets), industrial components, plumbing components (including, but not limited to, pipes, valves, accessories, manifolds, shower taps and shower valves), automotive components, and aerospace components (including, but not limited to, interior cabin components).

[0056] The article can be, for example, a portable electronic device component. As used herein, a "portable electronic device" refers to an electronic device that is conveniently carried in a variety of locations. Electricity transported and used Portable electronic devices may include, but are not limited to, mobile phones, personal digital assistants ("PDAs"), laptop computers, tablet computers, wearable computing devices (e.g., smart watches, smart glasses, etc.), cameras, portable audio players, portable radios, global positioning system receivers, and portable game consoles.

[0057] Portable electronic device components include, for example, radio antennas and Polymer Composition (PC) In this case, the wireless antenna can be a WiFi antenna or an RFID antenna. The portable electronic device component can also be an antenna housing.

[0058] In some embodiments, the portable electronic device component is an antenna housing. In some such embodiments, at least a portion of the radio antenna is disposed on the polymer composition (PC). Additionally or alternatively, at least a portion of the radio antenna can be detached from the polymer composition (PC). In some embodiments, the device component has a mounting hole or other fastening. mechanism It can be of an attachment component having a snap-fit ​​connector (including, but not limited to, a snap-fit ​​connector between itself and another component of the portable electronic device, including, but not limited to, a circuit board, a microphone, a speaker, a display, a battery, a cover, a housing, an electrical or electronic connector, a hinge, a wireless antenna, a switch, or a switch pad). In some embodiments, the portable electronic device can be at least a portion of the input device.

[0059] Examples of electrical and electronic devices are connectors, contactors and switches.

[0060] Polyamide (PA) or polymer compositions (PC) and articles prepared therefrom may also be used as gas barrier materials for packaging applications, in single or multi-layer articles.

[0061] Examples of oil and gas components include, but are not limited to, compressor rings, poppets, back-up seal rings, electrical connectors, labyrinth seals, motor end plates, bearings, bushings, suck rod guides, and downhole tubing.

[0062] Examples of automotive components include components in thermal management systems (including, but not limited to, thermostat housings, water inlet / outlet valves, water pumps, water pump impellers, and heater cores and end caps), air management system components (including, but not limited to, turbocharger actuators, turbocharger bypass valves, turbocharger hoses, EGR valves, CAC housings, exhaust gas recirculation systems, electronically controlled throttle valves, and hot air ducts), transmission components and launch device components (including, but not limited to, dual clutch transmissions, automated manual transmissions, continuously variable transmissions, automatic transmissions, torque converters, etc.), and other components in automotive components. automotive electronics, automotive lighting components (including but not limited to motor end caps, sensors, ECU housings, bobbins and solenoids, connectors, circuit protection / relays, actuator housings, Li-ion battery systems, and fuse boxes), traction motors and power electronic components (including but not limited to battery packs), fuel and selective catalytic reduction ("SCR") systems (including SCR module housings and connectors) , burnfluid system components (including, but not limited to, fuel flanges, rollover valves, quick connects, filter housings, fuel rails, fuel delivery modules, fuel hoses, fuel pumps, fuel injector O-rings, and fuel hoses); 、 Including, but not limited to, inlet and outlet valves and fluid pump components Fuel System Components ), interior components (e.g., dashboard components, display components, and installation components), and structural and lightweight components. quantity structure These include, but are not limited to, automotive components such as gears and bearings, sunroofs, brackets and mounts, electric battery housings, thermal management components, braking system elements, and pumps and EGR systems.

[0063] The articles can be molded from the polyamide (PA) or polymer composition (PC) by any process adapted for thermoplastics, such as extrusion, injection molding, blow molding, rotational molding or compression molding.

[0064] The goods are For example, polyamide (PA) or polymer composition (PC) can be printed by extruding the material when in the form of filaments and fused layers of filaments together, such as by Fused Filament Fabrication or Fused Deposition Modelling. Alternatively, polyamide (PA) or polymer composition (PC) can be in the form of a powder, such as a substantially spherical powder, and used in a laser process, such as Selective Laser Sintering. It is possible.

[0065] In some embodiments, the polyamide (PA) or polymer composition (PC) may be desirably incorporated into three-dimensional printing applications. One application is the manufacture of three-dimensional ("3D") objects using additive manufacturing systems. , Po providing a part material comprising a polyamide (PA) or a polymer composition (PC); and printing a layer of a three-dimensional object from the part material. is directed towards.

[0066] The polyamide (PA) or polymer composition (PC) can be incorporated into a composite material. The composite material comprises continuous reinforcing fibers embedded in a thermoplastic matrix. In some embodiments, the continuous reinforcing fibers are selected from glass fibers, carbon fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, aramid fibers, natural fibers (e.g., cotton, linen, and wood), and any combination of one or more thereof. Preferably, the continuous reinforcing fibers are glass fibers or carbon fibers. As used herein, continuous reinforcing fibers are reinforcing fibers having an average length in the longest dimension of at least 5 millimeters ("mm"), at least 10 mm, at least 25 mm, or at least 50 mm. The thermoplastic resin matrix comprises the polyamide (PA) or polymer composition (PC). The composite material can be a unidirectional composite material (e.g., a tape) or a multidirectional composite material (e.g., a woven fabric, a mat, or a layered fabric).

[0067] Use of polyamides (PA), polymer compositions (PC) and articles In some embodiments, the polyamide (PA), polymer composition (PC) or article is used as a portable electronic device component, as described above. Items such as can be used to prepare

[0068] Polyamide (PA) or polymer compositions (PC) can also be used to 3D print objects. EXAMPLES

[0069] The following examples demonstrate the heat and moisture wicking performance of the present polyamide (PA). As used in the examples, "E" refers to an example embodiment of the invention and "CE" refers to a counter example.

[0070] raw materials - HMDA: Obtained from Ascend Performance Materials (70%) - 1,10-diaminodecane ("DMDA"): obtained from Solvay (Novecare) - 1,3-BAC: obtained from Mitsubishi Gas Chemical Company, Inc. - Terephthalic Acid ("TA"): Obtained from Flint Hills Resources - Isophthalic Acid ("IA"): Obtained from Flint Hills Resources - Adipic Acid ("AA"): Obtained from Invista - 1,4-CHDA: Obtained from Eastman Chemical Company - 4-AMCC: obtained from Sigma-Aldrich - PA 6,T / 6,6 65 / 35: Obtained from Solvay Specialty Polymers USA, LLC - PA10, T / 10, I: Obtained from Kingfa (Vicnyl® 6100) - PA9,T: Obtained from Kuraray (Genestar TM GC 61210) - Impact Modifier: Obtained from Kraton Corporation (Kraton TM FG1901 GT, a linear triblock copolymer based on styrene and ethylene / butylene with a polystyrene content of 30% - Glass fiber:: chopped E-glass fiber (NEG HP 3610 manufactured by Nippon Electric Glass Co., Ltd.) - Additive package: consists of release agents, antioxidants and talc

[0071] Example 1 - Synthesis of polyamide and polymer compositions This example demonstrates the synthesis of a polyamide.

[0072] All of the copolyamides shown in Table 1 were prepared following a similar process using a 1 gallon autoclave reactor equipped with a distillate line fitted with a pressure regulating valve. As an example, in the preparation of copolyamide E1, the reactor was charged with 283 g DI water, 173 g hexamethylenediamine (70%), 116 g 1,10-diaminodecane, 242 g terephthalic acid, 22 g 1,4-cyclohexanedicarboxylic acid, 1.9 g acetic acid, and 0.16 g phosphorous acid. The reactor was sealed, purged with nitrogen, and heated to 260°C. The evolved water vapor was slowly released to maintain an internal pressure of 120 psig. The temperature was increased to 320°C. The reaction mixture was held at 320°C and the reactor pressure was reduced to atmospheric pressure. After an additional 60 minutes of holding, the polymer was discharged from the reactor.

[0073] E Similar to the following method for the preparation of 1, larger quantities of the copolyamide were was prepared. A stirred batch vessel was charged with 33.7 kg of deionized water, 21.58 kg of 70% hexamethylenediamine, 14.47 kg of 1,10-diaminodecane as a diamine component, and 30.11 kg of terephthalic acid and 2.71 kg of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid component. 、1 7.03 g phosphorous acid and 360.30 g glacial acetic acid too The mixture was heated at 150°C to obtain a salt solution. The contents were pumped continuously through a reactor zone maintained at about 180 psig and 220°C, then to a high pressure zone maintained at 300°C, and then through a tubular reactor at 100 psig heated to 350°C. The melt was fed into a twin screw extruder equipped with a forward vacuum vent. The finished polymer was extruded through a strand die into a water bath and chopped into pellets.

[0074] Sample parameters are shown in Table 1. For clarity, the number prefixes have been eliminated in the "Polyamide" column of Table 1. For example, 1,3-BAC is referred to as BAC in the "Polyamide" column of Table 1.

[0075] [Table 1]

[0076] In addition, polymer compositions were formed from the polymers in Table 1, as well as other polyamides, to demonstrate mechanical performance. Sample parameters are shown in Table 1A (all values ​​are in weight percent). The polyamide E5 used in the composition has an intrinsic viscosity (IV) of 1.15 dL / g as measured according to ASTM D5225.

[0077] [Table 2]

[0078] Example 2 - Thermal Performance To demonstrate thermal performance, Tm, Tg, Tc, enthalpy of fusion ("Hm"), and enthalpy of crystallization ("Hc") were measured. Tm and Tg were measured as described above. Tc, Hm, and Hc were measured according to ASTM D3418. Water absorption for the neat resin (see Table 2) was measured as follows: 2 inch diameter and 1 / 8 inch thick The disk samples were placed in boiling water and their weights were One The percent water absorption was measured periodically until it stabilized. ) / (Initial weight)) ×100 The water absorption reported in Table 2A was measured according to ASTM D570.

[0079] [Table 3]

[0080] [Table 4]

[0081] Referring to Table 2 、C E1, CE2 and E1 Comparisonunexpectedly demonstrate that the introduction of a relatively small amount of 1,4-CHDA (8 mol%) into PA 6T / 10T significantly increases the Tg (5°C) while maintaining high Tm and Tc. On the other hand, the introduction of a larger amount of 1,4-CHDA (20 mol%) , CE1 The introduction of 4-AMCC (5 mol %) reduces both Tg and Tm compared to PA 6T / 10T. Furthermore, comparisons CE2 and E3 show that a small amount of 4-AMCC significantly increases the Tg (7° C.) of PA 6T / 10T copolymer while maintaining high Tm and Tc. Comparisons CE2 and E4 show that a relatively small amount of 1,3-BAC (5 mol %) significantly increases the Tg (7° C.) of PA 6T / 10T copolymer while maintaining high Tg and Tc.

[0082] A small amount of alicyclic monomers containing cyclohexyl groups - Unlike Examples E1, E3, and E4, which contain ,stomach Softhalic acid (CE3 and CE7 The addition of small amounts of aromatic-containing diacids such as g and lowers Tm.

[0083] Example 3: Mechanical Performance To demonstrate the mechanical performance, tensile stress, tensile strain, weld tensile stress and weld tensile strain were measured according to ISO 527. Mechanical properties were measured on one-gate ("standard") and two-gate ("weld") injection molded samples to evaluate the effect of the weld line. The results are shown in Table 3.

[0084] [Table 5]

[0085] Referring to Table 3, E6 and E7 generally had improved mechanical properties compared to Examples CE8-CE11. Although resin E5 used in composition E6 comprises a lower content of flexible long chain diamine than the resins of compositions CE10 and CE11, composition E6 has higher strength and unexpectedly exhibits higher elongation and weld line strength compared to compositions CE10 and CE11. These improved mechanical properties are due to: Impact Modifier is introduced into composition E7.

[0086] The above embodiments are intended to be illustrative and not limiting. Additional embodiments are within the concept of the present invention. In addition, while the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the present invention. Any incorporation by reference of the above publications is limited such that no subject matter contrary to the express disclosure herein is incorporated.

Claims

1. - the below described: - 55 mol % to 75 mol % C ４ ~C ８ Aliphatic diamines, from 25 mol % to 45 mol % of C selected from the group consisting of 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine, 2-ethyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, and 1,12-diaminododecane; ９ ~C １２ Aliphatic diamines, from 0 mol % to 10 mol % of cycloaliphatic diamines containing cyclohexyl groups selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; A diamine component (A) comprising: a diamine component (A), wherein the mole percent is based on the total moles of diamine in said diamine component (A); - the below described: - 90% to 100% by mol of terephthalic acid, - 0 mol % to 10 mol % C ６ ~C １８ Aliphatic dicarboxylic acid or C different from terephthalic acid ８ ~C １８ Aromatic dicarboxylic acids, and - 0 mol % to 10 mol % of cyclohexanedicarboxylic acid wherein the mole percentages are based on the total moles of dicarboxylic acid in said dicarboxylic acid component (B); - the below described: an amino acid component (C) comprising from 0 mol % to 9 mol % of 4-aminomethylcyclohexanecarboxylic acid, The molar percentage of the dicarboxylic acid in the dicarboxylic acid component (B) is based on the total molar number of the dicarboxylic acid in the dicarboxylic acid component (B), Including, at least one of the alicyclic diamine, the cyclohexane dicarboxylic acid, and the 4-aminomethylcyclohexane carboxylic acid has a concentration greater than 0.5 mole percent; A polyamide (PA) formed from the polycondensation of a reaction mixture (RM).

2. Said C ４ ~C ８ 2. Polyamide (PA) according to claim 1, wherein the aliphatic diamine is selected from the group consisting of 1,4-diaminobutane ("putrescine"), 1,5-diaminopentane ("cadaverine"), 2-methyl-1,5-diaminopentane, hexamethylenediamine ("HMDA"), 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 1,7-diaminoheptane and 1,8-diaminooctane.

3. The polyamide (PA) according to claim 2, wherein the C4-C8 aliphatic diamine is HMDA.

4. Said C ９ ~C １２ The polyamide (PA) according to any one of claims 1 to 3, wherein the aliphatic diamine is 1,10-diaminodecane.

5. Said C ６ ~C １８ Polyamide (PA) according to any one of claims 1 to 4, wherein the aliphatic dicarboxylic acid is selected from the group consisting of 2,2-dimethyl-glutaric acid, adipic acid, 2,4,4-trimethyl-adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid and octadecanedioic acid.

6. The above-mentioned C different from terephthalic acid ８ ~C １８ The polyamide (PA) according to any one of claims 1 to 5, wherein the aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, naphthalenedicarboxylic acid, 4,4'-bibenzoic acid, 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)ketone, 4,4'-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)ketone, bis(3-carboxyphenoxy)benzene.

7. 7. Polyamide (PA) according to any one of claims 1 to 6, wherein only one of the alicyclic diamine, the cyclohexanedicarboxylic acid and the 4-aminomethylcyclohexanecarboxylic acid has a concentration in the reaction mixture (RM) of greater than 0.5 mol %, and wherein the reaction mixture (RM) does not contain the other two alicyclic monomers containing a cyclohexyl group.

8. The reaction mixture (RM) is ６ ~C １８ Aliphatic dicarboxylic acid and / or C different from terephthalic acid ８ ~C １８ Polyamide (PA) according to any one of claims 1 to 7, which is free of aromatic dicarboxylic acids.

9. A polyamide (PA) described in any one of claims 1 to 8, wherein the polyamide (PA) is semi-crystalline.

10. A polyamide (PA) according to any one of claims 1 to 9, wherein the polyamide (PA) is semi-crystalline and exhibits a heat of fusion of at least 30 J / g measured according to ASTM D3418.

11. A polyamide (PA) according to any one of claims 1 to 10, wherein the polyamide (PA) exhibits a glass transition temperature Tg of at least 110°C measured according to ASTM D3418.

12. A polyamide (PA) according to any one of claims 1 to 11, wherein the polyamide (PA) exhibits a melting temperature Tm of at least 290°C measured according to ASTM D3418.

13. - a polyamide (PA) according to any one of claims 1 to 12, 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, halogen-free flame retardants, nucleating agents and antioxidants; A polymer composition (PC) comprising:

14. The polymer composition (PC) according to claim 13, comprising 10% to 60% by weight of glass fibres, based on the total weight of said polymer composition (PC).

15. 15. A polymer composition (PC) according to claim 13 or 14, comprising more than 30% and less than 99.95% by weight of said polyamide (PA).

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