US2016222210A1PendingUtilityA1

Transparent polyamide-imides

54
Assignee: EMS PATENT AGPriority: Sep 12, 2012Filed: Apr 11, 2016Published: Aug 4, 2016
Est. expirySep 12, 2032(~6.2 yrs left)· nominal 20-yr term from priority
C08L 79/08C08K 7/02C08G 73/14C08G 73/1075C08K 3/00C08K 7/14C08L 77/02C08G 69/00C08K 3/26C08K 3/346C08K 3/22C08L 77/00Y10T428/139C08K 3/40C08K 3/08C08K 3/34C08K 3/30
54
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Claims

Abstract

What is described is a transparent polyamide-imide based on one or more different imido-dicarboxylic acids (AB) or derivatives thereof, and cycloaliphatic diamines (C) comprising 6 to 24 carbon atoms, wherein the imido-dicarboxylic acids (AB) or derivatives thereof are selected from the group of imido-dicarboxylic acids (AB) having the following structural formulas: wherein: ASL=(CH 2 ) 5-11 , phenylene, (ylomethyl)phenyl, bis(ylomethyl)benzene, cyclohexanediyl, (ylomethyl)cyclohexyl, bis(ylomethyl)cyclohexane, cyclopentanediyl, (ylomethyl)cyclopentyl, bis(ylomethyl)cyclopentane, R═OH, O-alkyl, O-aryl, Cl, NH-ASL-COOH, Br, O—(CO)-alkyl, O—(CO)-aryl, R1=H, methyl, ethyl, propyl, with the provision that the ring can be substituted once or twice, and, with double substitution of the ring, the two substituents can be selected from the group, but may be different, and also moulding compounds based thereon, a method for production, and uses.

Claims

exact text as granted — not AI-modified
1 - 16 . (canceled) 
     
     
         17 . A thermoplastic moulding compound based on a polyamide-imide, characterised by the following composition:
 (F1) 30-100% by weight of at least one transparent polyamide-imide based on one or more different imido-dicarboxylic acids (AB) or derivatives thereof,
 and cycloaliphatic diamines (C) comprising 6 to 24 carbon atoms, selected from the group consisting of: bis-(4-amino-3-methyl-cyclohexyl)-methane (MACM), bis-(4-amino-cyclohexyl)-methane (PACM), bis-(4-amino-3-ethyl-cyclohexyl)-methane (EACM), bis-(4-amino-3,5-dimethy-cyclohexyl)-methane (TMDC), 2,6-norbornanediamine, 2,6-bis-(aminomethyl)-norbornane, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, bis-(1,3-aminomethyl)cyclohexane, isophoronediamine, cyclohexanediamine, 1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane, isophoronediamine, norbornanedimethylamine, 2,2-(4,4′-diaminodicyclohexyl)propane (PACP) or mixtures of these cycloaliphatic diamines, wherein the imido-dicarboxylic acids (AB) or derivatives thereof are selected from the group of imido-dicarboxylic acids (AB) having the following structural formulas: 
   
       
         
           
           
               
               
           
         
       
       wherein:
   ASL=(CH 2 ) 9-11 , phenylene, (ylomethyl)phenyl, bis(ylomethyl)benzene, cyclohexanediyl, (ylomethyl)cyclohexyl, bis(ylomethyl)cyclohexane, cyclopentanediyl, (ylomethyl)cyclopentyl, bis(ylomethyl)cyclopentane,   R═OH, O-alkyl, O-aryl, Cl, NH-ASL-COOH, Br, O—(CO)-alkyl, O—(CO)-aryl,   R1═H, methyl, ethyl, propyl, with the provision that the ring can be substituted once or twice, and, with double substitution of the ring, the two substituents can be selected from the group, but may be different;   with the proviso that the transparent polyamide-imide is free from building blocks in which said cycloaliphatic diamines (C) are, with at least one amino-group thereof, forming the imido-element of imido-aminocarboxylic acids corresponding to said imido-dicarboxylic acids (AB) and in which said cycloaliphatic diamines (C) are replacing the structural element N-ASL-COR therein,   and with the proviso that the transparent polyamide-imide is free from aromatic diamines   
 (F2) 20-60% by weight of reinforcing agents and/or fillers 
 (F3) 0-50% by weight of additives and/or further polymers, different from the polyamide-imide, 
 wherein the components A to C together give 100% 
 with the proviso that the thermoplastic moulding compound is not curable or crosslinkable at a temperature of 240-290° C., and is also not cured or cross-linked at a temperature of 240-290° C. 
 
     
     
         18 . The thermoplastic moulding compound according to  claim 17 , wherein it is based exclusively on
 a diacid part, exclusively based on   20-100 mol-% of one or more of said imido-dicarboxylic acids (AB) or derivatives thereof 0-80 mol-% of at least one further diacid (D), different from said imido-dicarboxylic acids (AB), wherein the diacid parts supplement to 100 mol-%;   and a diamine part, exclusively based on   20-100 mol-% of at least one of said cycloaliphatic diamines (C) comprising 6 to 24 carbon atoms,   0-80 mol-% of at least one further, non-aromatic diamine (E), different from said cycloaliphatic diamines (C)   wherein the diamine parts supplement to 100 mol-%.   
     
     
         19 . The thermoplastic moulding compound according to  claim 17 , wherein it is exclusively based on one or more of said imido-dicarboxylic acids (AB) or derivatives thereof, and said cycloaliphatic diamines (C) comprising 6 to 24 carbon atoms. 
     
     
         20 . The thermoplastic moulding compound according to  claim 17 , wherein at least one imido-dicarboxylic acid (AB) or derivative thereof, in the polyamide-imide corresponds to the following structural formula: 
       
         
           
           
               
               
           
         
       
     
     
         21 . The thermoplastic moulding compound according to  claim 17 , wherein a cycloaliphatic or aromatic tricarboxylic acid (A) or derivatives thereof, forming the imido-dicarboxylic acid (AB) or derivative thereof at least in part, is selected from the group consisting of: cyclopentane-1,2,4-tricarboxylic acid, 2-methyl-cyclopentane-1,2,4-tricarboxylic acid, 3-methyl-cyclopentane-1,2,4-tricarboxylic acid, 3,5-dimethyl-cyclopentane-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, 2-methyl-cyclohexane-1,2,4-tricarboxylic acid, 3-methyl-cyclohexane-1,2,4-tricarboxylic acid, 4-methyl-cyclohexane-1,2,4-tricarboxylic acid, 5-methyl-cyclohexane-1,2,4-tricarboxylic acid, 1,2-dimethyl-cyclohexane-1,2,4-tricarboxylic acid, 3,5-dimethyl-cyclohexane-1,2,4-tricarboxylic acid, 2,4-dimethyl-cyclohexane-1,2,4-tricarboxylic acid, or a mixture thereof. 
     
     
         22 . The thermoplastic moulding compound according to  claim 17 , wherein the molar ratio in the overall polyamide-imide of a cycloaliphatic or aromatic tricarboxylic acid (A) or derivatives thereof, or, with a mixture of different cycloaliphatic or aromatic tricarboxylic acids (A) or derivatives thereof, the sum of these tricarboxylic acids, forming the imido-dicarboxylic acid (AB) or derivative thereof at least in part, to an aminocarboxylic acid or lactam (B), or, with a mixture of different such aminocarboxylic acids or lactams (B), the sum of these systems, forming the imido-dicarboxylic acid (AB) or derivative thereof at least in part, lies in the range from 1:2.5 to 1:1. 
     
     
         23 . The thermoplastic moulding compound according to  claim 17 , wherein the molar ratio in the polyamide-imide of at least one imido-dicarboxylic acid (AB) or derivative thereof, or, with a mixture of different imido-dicarboxylic acids (AB) or derivatives thereof, the sum of these dicarboxylic acids, to the cycloaliphatic diamine (C), or, with a mixture of different cycloaliphatic diamines (C), to the sum of these diamines, lies in the range from 1.5:1 to 1:1.5 and/or wherein the polyamide-imide is formed on the basis of at least one further diacid (D), different from the component (AB), wherein, in the overall polyamide-imide, the diacid proportion formed from the component (AB) makes up at least 20 mol %, and the rest making 100 mol % is formed by the component (D). 
     
     
         24 . The thermoplastic moulding compound according to  claim 17 , wherein the polyamide-imide is formed on the basis of at least one further diamine (E), different from the component (C), wherein, in the overall polyamide-imide, the diamine proportion formed from the component (C) makes up at least 20 mol % and the rest making up 100 mol % is formed by the component (E). 
     
     
         25 . The thermoplastic moulding compound according to  claim 17 , wherein the imido-dicarboxylic acid (AB) is selected from the group consisting of: trimellitic imido-caproic acid, trimellitic imido-undecanoic acid, trimellitic imido-lauric acid, or a mixture thereof, and in that the cycloaliphatic diamine (C) is selected from the group consisting of: bis-(4-amino-3-methyl-cyclohexyl)-methane (MACM), bis-(4-amino-cyclohexyl)-methane (PACM), or a mixture thereof. 
     
     
         26 . The thermoplastic moulding compound according to  claim 17 , wherein the polyamide-imide is formed on the basis of at least one further diacid (D), different from the component (AB), and this further dicarboxylic acid (D) is terephthalic acid, isophthalic acid, adipic acid, or cyclohexane-1,3-dicarboxylic acid, or a mixture thereof. 
     
     
         27 . The thermoplastic moulding compound according to  claim 17 , wherein, as component (F2), fibrous and/or particulate reinforcing agents and/or fillers are added. 
     
     
         28 . The thermoplastic moulding compound according to  claim 17 , wherein, as component (F3), stabilisers, nucleation agents, processing aids and/or impact toughness modifiers are contained. 
     
     
         29 . An object having at least one region or a layer formed from a thermoplastic moulding compound according to  claim 17 , wherein said object is a film, an insert part, a profile, a tube, a hollow body, an optically variable filter, an optical lens. 
     
     
         30 . A method for producing a polyamide-imide from a thermoplastic moulding compound according to  claim 17 , wherein, in a first reaction step, an imido-dicarboxylic acid (AB) selected from the group of imido-dicarboxylic acids (AB) having the following structural formulas: 
       
         
           
           
               
               
           
         
       
       wherein:
 ASL=(CH 2 ) 9-11 , phenylene, (ylomethyl)phenyl, bis(ylomethyl)benzene, cyclohexanediyl, (ylomethyl)cyclohexyl, bis(ylomethyl)cyclohexane, cyclopentanediyl, (ylomethyl)cyclopentyl, bis(ylomethyl)cyclopentane, 
 R═OH, O-alkyl, O-aryl, Cl, NH-ASL-COOH, Br, O—(CO)-alkyl, O—(CO)-aryl, 
 R1═H, methyl, ethyl, propyl, with the provision that the ring can be substituted once or twice, and, with double substitution of the ring, the two substituents can be selected from the group, but may be different 
 is formed starting from the corresponding cycloaliphatic or aromatic tricarboxylic acids having at least two vicinal carboxyl groups (A) or derivatives thereof and amino carboxylic acid or lactam (B), and, in a second subsequent and separate step, these imido-dicarboxylic acids (AB) or derivatives thereof are reacted with said cycloaliphatic diamines (C) comprising 6 to 24 carbon atoms, and optionally further diacids (D), different from the component (AB), and/or further diamines (E), different from the component (C), to form the polyamide-imide. 
 
     
     
         31 . The thermoplastic moulding compound according to  claim 17 , wherein the entire proportion of imido-dicarboxylic acid (AB) or derivative thereof, in the polyamide-imide corresponds to the following structural formula: 
       
         
           
           
               
               
           
         
         wherein, R1═H and/or ASL=(CH 2 ) 5-11  and/or R═OH, NH-ASL-COOH. 
       
     
     
         32 . The thermoplastic moulding compound according to  claim 17 , wherein the imido-dicarboxylic acid (AB) or derivative thereof is selected from the group consisting of: trimellitic imido-caproic acid, trimellitic imido-undecanoic acid, trimellitic imido-dodecanoic acid, or derivatives thereof where R═O-alkyl, O-aryl, Cl, Br, NH-ASL-COOH, O—(CO)-alkyl, O—(CO)-aryl, or a mixture thereof. 
     
     
         33 . The thermoplastic moulding compound according to  claim 17 , wherein a cycloaliphatic or aromatic tricarboxylic acid (A) or derivatives thereof in the form of acid chlorides, esters or anhydrides, forming the imido-dicarboxylic acid (AB) or derivative thereof at least in part, is selected from the group consisting of: cyclopentane-1,2,4-tricarboxylic acid, 2-methyl-cyclopentane-1,2,4-tricarboxylic acid, 3-methyl-cyclopentane-1,2,4-tricarboxylic acid, 3,5-dimethyl-cyclopentane-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, 2-methyl-cyclohexane-1,2,4-tricarboxylic acid, 3-methyl-cyclohexane-1,2,4-tricarboxylic acid, 4-methyl-cyclohexane-1,2,4-tricarboxylic acid, 5-methyl-cyclohexane-1,2,4-tricarboxylic acid, 1,2-dimethyl-cyclohexane-1,2,4-tricarboxylic acid, 3,5-dimethyl-cyclohexane-1,2,4-tricarboxylic acid, 2,4-dimethyl-cyclohexane-1,2,4-tricarboxylic acid, or a mixture thereof. 
     
     
         34 . The thermoplastic moulding compound according to  claim 17 , wherein the molar ratio in the overall polyamide-imide of a cycloaliphatic or aromatic tricarboxylic acid (A) or derivatives thereof, or, with a mixture of different cycloaliphatic or aromatic tricarboxylic acids (A) or derivatives thereof, the sum of these tricarboxylic acids, forming the imido-dicarboxylic acid (AB) or derivative thereof at least in part, to an aminocarboxylic acid or lactam (B), formed as an aliphatic aminocarboxylic acid or aliphatic lactam (B) comprising 6-12 carbon atoms, or, with a mixture of different such aminocarboxylic acids or lactams (B), the sum of these systems, forming the imido-dicarboxylic acid (AB) or derivative thereof at least in part, lies in the range from 1:1.5 to 1:1. 
     
     
         35 . The thermoplastic moulding compound according to  claim 17 , wherein the cycloaliphatic diamine (C) is selected from the group consisting of: bis-(4-amino-3-methyl-cyclohexyl)methane (MACM), bis-(4-amino-cyclohexyl)-methane (PACM), or mixtures thereof. 
     
     
         36 . The thermoplastic moulding compound according to  claim 17 , wherein the polyamide-imide is formed on the basis of at least one further diacid (D), different from the component (AB), wherein, in the overall polyamide-imide, the diacid proportion formed from the component (AB) lies in the range from 30 to 70 mol %, and the rest making 100 mol % is formed by the component (D), wherein the component (D) is selected from the following group: bifunctional, aliphatic, cycloaliphatic or aromatic dicarboxylic acids, selected from the group: adipic acid, suberic acid, azelaic acid, sebacic acid, undecane diacid, dodecane diacid, tridecane diacid, tetradecane diacid, pentadecane diacid, hexadecane diacid, heptadecane diacid, octadecane diacid, C36-dimer fatty acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, cis- and/or trans-cyclohexane-1,4-dicarboxylic acid and/or cis- and/or trans-cyolohexane-1,3-dicarboxylic acid (CHDA), and mixtures thereof. 
     
     
         37 . The thermoplastic moulding compound according to  claim 17 , wherein the polyamide-imide is formed on the basis of at least one further diamine (E), different from the component (C), wherein, in the overall polyamide-imide, the diamine proportion formed from the component (C) makes up 30 to 70 mol %, and the rest making up 100 mol % is formed by the component (E), wherein the component (E) is selected from the following group: linear or branched aliphatic diamine, from the following group: 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,8-octanediamine, 2-methyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1-15-pentadecanediamine, 1,16-hexadecanediamine, 1-17-heptadecanediamine, 1-18-octadecanediamine, meta-xylylenediamine and para-xylylenediamine, or mixtures thereof. 
     
     
         38 . The thermoplastic moulding compound according to  claim 17 , wherein the imido-dicarboxylic acid (AB) is selected from the group consisting of: trimellitic imido-caproic acid, trimellitic imido-undecanoic acid, trimellitic imido-lauric acid, or a mixture thereof, and in that the cycloaliphatic diamine (C) is selected from the group consisting of: bis-(4-amino-3-methyl-cyclohexyl)-methane (MACM), bis-(4-amino-cyclohexyl)-methane (PACM), or a mixture thereof, or just bis-(4-amino-3-methyl-cyclohexyl)-methane (MACM), wherein the molar ratio in the polyamide-imide of imido-dicarboxylic acid (AB), or, with a mixture of different imido-dicarboxylic acids (AB), the sum of these dicarboxylic acids, to the cycloaliphatic diamine (C), or, with a mixture of different cycloaliphatic diamines (C), to the sum of these diamines, lies substantially at 1:1. 
     
     
         39 . A thermoplastic moulding compound according to  claim 17 , characterised by the following composition:
 (F1) 30-100% by weight of said at least one polyamide-imide   (F2) 20-60% by weight of reinforcing agents and/or fillers   (F3) 0-50% by weight of additives and/or further polymers, different from the polyamide-imide,   wherein the components A to C together give 100%.   
     
     
         40 . The thermoplastic moulding compound according to  claim 27 , wherein, as component (F2), fibrous and/or particulate reinforcing agents and/or fillers are added, selected from the group consisting of: glass fibres, carbon fibres, metal or plastic fibres, wherein these may have a round or flat cross section, fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicic acids, magnesium carbonate, magnesium hydroxide, chalk, lime, feldspar, barium sulphate, solid or hollow glass balls or ground glass, permanently magnetic or magnetisable metal compounds and/or alloys, wherein the fillers surface-treated or surface untreated. 
     
     
         41 . The thermoplastic moulding compound according to  claim 27 , wherein, as component (F3), stabilisers, nucleation agents, processing aids and/or impact toughness modifiers are contained, wherein in the range between 5 and 30% by weight of one or more impact toughness modifiers are contained. 
     
     
         42 . An object having at least one region or a layer formed from the thermoplastic moulding compound according to  claim 17 , wherein said object is a film, an insert part, a profile, a tube, a hollow body, an optically variable filter, an ophthalmic lens, and wherein the light transmission is at least 88%. 
     
     
         43 . A method for producing a polyamide-imide for a thermoplastic moulding compound according to  claim 17 , wherein, in a first reaction step, an imido-dicarboxylic acid (AB) selected from the group of imido-dicarboxylic acids (AB) having the following structural formulas: 
       
         
           
           
               
               
           
         
       
       wherein:
 ASL=(CH 2 ) 5-11 , phenylene, (ylomethyl)phenyl, bis(ylomethyl)benzene, cyclohexanediyl, (ylomethyl)cyclohexyl, bis(ylomethyl)cyclohexane, cyclopentanediyl, (ylomethyl)cyclopentyl, bis(ylomethyl)cyclopentane, 
 R═OH, O-alkyl, O-aryl, Cl, NH-ASL-COOH, Br, O—(CO)-alkyl, O—(CO)-aryl, 
 R1═H, methyl, ethyl, propyl, with the provision that the ring can be substituted once or twice, and, with double substitution of the ring, the two substituents can be selected from the group, but may be different 
 is formed starting from the corresponding cycloaliphatic or aromatic tricarboxylic acids having at least two vicinal carboxyl groups (A) or derivatives thereof and amino carboxylic acid or lactam (B), and, in a second subsequent and separate step, these imido-dicarboxylic acids (AB) or derivatives thereof are reacted with said cycloaliphatic diamines (C) comprising 6 to 24 carbon atoms, and optionally further diacids (D), different from the component (AB), and/or further, non-aromatic diamines (E), different from the component (C), to form the polyamide-imide.

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