Molding compound containing polyether block amide (PEBA)

Abstract

A molding compound contains polyether block amide (PEBA) based on a subunit 1 made of at least one linear aliphatic diamine having 5 to 15 C atoms and at least one linear aliphatic or aromatic dicarboxylic acid having 6 to 16 C atoms. The PEBA also contains a subunit 2 made of at least one polyether diol having at least 3 C atoms per ether oxygen and primary OH groups at the chain ends. The sum of the C atoms of diamine and dicarboxylic acid is odd and is 19 or 21, and the number-average molar mass of the subunit 2 is 200 to 900 g/mol. A molded object can be created from the molding compound, which can be a molded part, a film, a bristle, a fiber, or a foam.

Claims

1. A moulding composition, comprising: polyether block amide (PEBA) having a subunit 1 and a subunit 2, wherein the subunit 1 comprises at least one linear aliphatic diamine containing 5 to 15 carbon atoms and at least one linear aliphatic dicarboxylic acid containing 6 to 16 carbon atoms, the subunit 2 comprises at least one polyether diol selected from the group consisting of polypropane-1,3-diol, polytetramethylene glycol, and mixtures thereof, a sum total of the carbon atoms from the diamine and the dicarboxylic acid is 19 or 21 carbon atoms; and a number-average molar mass of the subunit 2 is 400-700 g/mol and subunit 1 has a number-average molar mass of 500 to 1,800 g/mol, and a haze value of the PEBA is about 66 or lower, as measured by means of 60602 mm plaques to ASTM standard D 1003 using a Konica-Minolta CM-3600d.

2. The moulding composition according to claim 1, wherein the number of carbon atoms in the diamine is an even number and the number of carbon atoms in the dicarboxylic acid is an odd number.

3. The moulding composition according to claim 1, wherein the sum total of the carbon atoms from diamine and dicarboxylic acid is 19.

4. The moulding composition according to claim 1, wherein the subunit 1 is selected from the group consisting of nylon-6,13, nylon-10,9, and nylon-12,9.

5. The moulding composition according to claim 1, wherein the linear aliphatic diamine has 6 to 12 carbon atoms.

6. The moulding composition according to claim 1, wherein the dicarboxylic acid has 6 to 14 carbon atoms.

7. A moulded article, produced from the moulding composition according to claim 1.

8. The moulded article according to claim 7, wherein said article is a moulding, a film, a bristle, a fibre, or a foam.

9. The moulded article according to claim 7, wherein the moulded article is produced by a process selected from the group consisting of compression-moulding, foaming, extrusion, coextrusion, blow moulding, 3D blow moulding, coextrusion blow moulding, coextrusion 3D blow moulding, coextrusion suction blow moulding, and injection moulding.

10. The moulded article according to claim 7, wherein said article is a fibre composite component, a shoe sole, a top sheet for skis or snowboards, a spectacle frame, a design article, a sealing material, a body protection, an insulating material, or a housing part provided with a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) In one preferred embodiment, the number-average molar mass of the subunit 1 is 250 to 4500 g/mol, more preferably 400 to 2500 g/mol, even more preferably 400 to 2000 g/mol, most preferably 500 to 1800 g/mol. This leads to a material with higher translucency and simultaneously reduced formation of deposits.

(2) The polyether diol of the PEBA is preferably selected from polypropane-1,3-diol, polytetramethylene glycol and mixtures thereof.

(3) The sum total of the carbon atoms from diamine and dicarboxylic acid in the PEBA is an odd number. It is 19 or 21. Preferably, the sum total is 19.

(4) It is furthermore preferable for the number of carbon atoms in the diamine to be an even number and for the number of carbon atoms in the acid to be an odd number.

(5) Suitable polyamides of subunit 1 are selected, by way of example, from 5,14, 5,16, 6,13, 6,15, 7,12, 7,14, 8,11, 8,13, 9,10, 9,12, 10,9, 10,11, 11,8, 11,10, 12,7, 12,9, 13,6, 13,8. It is furthermore preferable for the subunit 1 to be selected from nylon-6,13, nylon-10,9 and nylon-12,9.

(6) The invention further provides a moulded article produced from the moulding composition according to the invention. The moulded article is preferably a moulding, a film, a bristle, a fibre or a foam. The moulded article may for example be produced by compression-moulding, foaming, extrusion, coextrusion, blow moulding, 3D blow moulding, coextrusion blow moulding, coextrusion 3D blow moulding, coextrusion suction blow moulding or injection moulding. Processes of this kind are known to those skilled in the art.

(7) The invention further provides the use of the moulded article according to the invention, which may for example be used as a fibre composite component, shoe sole, top sheets for skis or snowboards, line for media, spectacle frame, design article, sealing material, body protection, insulating material or housing part provided with a film.

EXAMPLES

(8) Preparation of the Polyether Block Amides (PEBA)

(9) General Procedure for Preparing the PEBA:

(10) The diamine, 10% of the mass thereof of deionized (DI) water, dicarboxylic acid and the polyether diol polytetrahydrofuran (PTHF) are initially charged successively at below 60 C. in the feed tank of a 100-1 double-tank polycondensation installation, provided with an anchor stirrer. PTHF forms the subunit 2. Based on the polyether diol, 0.1% Irganox 1098 (BASF SE) is added as process stabilizer. Based on the total solids content, 0.3% 50%-strength hypophosphorous acid is added as catalyst. After repeated pressure inertization with N.sub.2, the tank contents are heated to 180 C.-190 C.; at 160 C. the stirrer is engaged. The starting materials are stirred for 1 hour and are thereafter transferred into the polycondensation reactor, provided with a helical stirrer and torque recorder. After pressure has been equalized between the two vessels, the reactor valve is closed and the contents are brought up to 245 C. within 6 hours under stirring at 25 rpm. Upon reaching 21 bar autogenous pressurenormally between 210 C. and 225 C. internal temperaturea two-hour pressure maintenance stage is observed, after which depressurization is performed continuously to atmospheric pressure under further raising of the temperature. After 3-4 hours at atmospheric pressure, reduced pressure is applied within 5 hours until a final reduced pressure of 40-60 mbar is reached. Further stirring is performed under these conditions until the desired final torque is reached. The melt is extruded into a water bath, pelletized and dried at 70 C.-90 C. in a tumble dryer to a water content<0.1%.

(11) Molar Ratio of Subunit 1 to Subunit 2:

(12) Examples 1 to 14, 51-55 and 58-80: 100:103; Examples 15-35, 48-50 and 58-57: 100:102; Examples 38-40: 100:105.

(13) Subsequent to drying according to the process described in DE4301801A1 in solid phase at 130 C.-135 C., 0.95 wt. % of a stabilizer mixture, based on the total weight of PEBA and stabilizer, was added to some of the PEBA (hereinafter identified with st).

(14) The PEBA prepared are summarized in Table 1 which follows. The molar mass of the subunit 1 results from the molar ratio of the dicarboxylic acid used and the diamine.

(15) TABLE-US-00001 TABLE 1 PEBA prepared Initial Initial Initial weight of weight weight of Dicarboxylic dicarboxylic Mn of Mn of of Experimerit Diamine diamine acid acid subunit 1 pTHF pTHF Product 1 6 11.999 10 23.694 2300 650 9.286 PEBA 6.10 2 6 8.823 10 20.186 1100 650 15.955 PEBA 6.10 3 6 7.16 10 18.35 800 650 19.447 PEBA 6.10 4 6 11.999 10 23.694 2300 650 9.286 PEBA 6.10-st 5 6 8.823 10 20.186 1100 650 15.955 PEBA 6.10-st 6 6 7.16 10 18.35 800 650 19.447 PEBA 6.10-st 7 6 10.35 13 25.219 2300 650 9.4 PEBA 6.13 8 6 7.396 13 21.446 1100 650 16.122 PEBA 6.13 9 6 5.848 13 19.476 800 650 19.632 PEBA 6.13 10 6 4.379 13 17.606 600 650 22.964 PEBA 6.13 11 6 10.36 13 25.219 2300 650 9.4 PEBA 6.13-st 12 6 7.395 13 21.446 1100 650 16.122 PEBA 6.13-st 13 6 5.848 13 19.476 800 650 19.632 PEBA 6.13-st 14 6 4.379 13 17..606 600 650 22.964 PEBA 6.13-st 15 10 14.986 10 20.472 2268 650 9.521 PEBA 10.10 16 10 10.927 10 17.755 1083 650 16.282 PEBA 10.10 17 10 8.758 10 16.303 780 650 19.894 PEBA 10.10 19 10 15.296 13 23.832 4096 650 5.859 PEBA 10.13 20 10 13.176 13 22.196 2268 650 9.607 PEBA 10.13 21 10 11.211 13 20.68 1509 650 13.08 PEBA 10.13 22 10 9.243 13 19.162 1068 650 16.558 PEBA 10.13 23 10 15.296 13 23.832 4096 650 5.859 PEBA 10.13-st 24 10 13.176 13 22.196 2268 650 9.607 PEBA 10.13-st 25 10 11.211 13 20.68 1509 650 13.08 PEBA 10.13-st 26 10 9.243 13 19.162 1068 650 16.558 PEBA 10.13-st 27 10 17.959 9 21.246 4096 650 5.781 PEBA 10.9 28 10 15.685 9 19.806 2268 650 9.487 PEBA 10.9 29 10 13.574 9 18.469 1509 650 12.928 PEBA 10.9 30 10 11.455 9 17.128 1068 650 16.38 PEBA 10.9 31 10 7.481 9 14.612 600 650 22.856 PEBA 10.9 32 10 17.959 9 21.246 4096 650 5.781 PEBA 10.9-st 33 10 15.685 9 19.806 2268 650 9.487 PEBA 10.9-st 34 10 13.574 9 18.469 1509 650 12.928 PEBA 10.9-st 35 10 11.455 9 17.128 1068 650 16.38 PEBA 10.9-st 36 6 11.111 13 25.38 4000 1000 8.449 PEBA 6.13 37 6 9.31 13 22.664 2300 1000 12.934 PEBA 6.13 38 6 6.197 13 17.971 1100 1000 20.684 PEBA 6.13 39 6 11.111 13 25.38 4000 1000 8.449 PEBA 6.13-st 40 6 5.197 13 17.971 1100 1000 20.684 PEBA 5.13-st 48 6 6.056 9 16.202 600 650 22.691 PEBA 6.9-st 49 6 9.310 9 19.602 1083 650 16.052 PEBA 6.9-st 50 6 10.924 9 21.288 1509 650 12.760 PEBA 6.9-st 51 7 11.053 10 21.058 1509 650 12.861 PEBA 7.10 52 5 9.702 12 24.409 1760 650 11.493 PEBA 5.12 53 7 9.952 12 22.065 1509 650 12.954 PEBA 7.12 54 7 5.095 12 16.917 600 650 22.937 PEBA 7.12 55 7 9.014 14 22.923 1509 650 13.034 PEBA 7.14 56 12 12.410 9 16.251 1083 650 15.302 PEBA 12.9-st 57 12 8.030 9 14.000 600 650 22.919 PEBA 12.9-st 58 6 8.789 13 23.219 1509 650 12.963 PEBA 6.13-st 59 7 9.465 13 22.510 1509 650 12.996 PEBA 7.13 60 7 4.710 13 17.246 600 650 22.993 PEBA 7.13 All initial weights in kg diamine 5 =1,5-diaminopentane diamine 6 = hexamethylenediamine diamine 7 = 1,7-diaminoheptane diamine 10 = 1,10-decamethylenediamine dicarboxylic acid 9 = azelaic acid dicarboxylic acid 10 = sebacic acid dicarboxylic acid 12 = dodecanedioic acid dicarboxylic acid 13 = brassylic acid dicarboxylic acid 14 = tetradecanedieic acid pTHF = polytetrahydrofuran suffix st: stabilized with stabilizer mixture

(16) The PEBA prepared were investigated in respect of appearance of the extrudate, relative viscosity .sub.rel and melting point Tm (cf. Table 2). Appearance of the extrudate: visual inspection. Viscosity: ISO 307. Tm: DSC, second heating step to ISO 11357.

(17) TABLE-US-00002 TABLE 2 Properties of the PEBA prepared Appearance of Tm (DSC, second Experiment Product the extrudate .sub.rel heating step) 1 PEBA 6.10 translucent 1.81 219 2 PEBA 6.10 translucent 1.83 214 3 PEBA 6.10 translucent 1.96 210 4 PEBA 6.10-st translucent 1.81 219 5 PEBA 6.10-st translucent 1.83 214 6 PEBA 6.10-st translucent 1.96 210 7 PEBA 6.13 translucent 1.87 199 8 PEBA 6.13 translucent 1.84 195 9 PEBA 6.13 translucent 1.9 191 10 PEBA 6.13 translucent 1.96 185 11 PEBA 6.13-st translucent 1.87 199 12 PEBA 6.13-st translucent 1.84 195 13 PEBA 6.13-st translucent 1.9 191 14 PEBA 6.13-st translucent 1.96 185 15 PEBA 10.10 translucent 1.75 194 16 PEBA 10.10 translucent 1.94 184 17 PEBA 10.10 translucent 1.85 179 19 PEBA 10.13 translucent 1.9 166 20 PEBA 10.13 translucent 1.85 172 21 PEBA 10.13 translucent 1.83 175 22 PEBA 10.13 translucent 1.9 164 23 PEBA 10.13-st translucent 1.9 166 24 PEBA 10.13-st translucent 1.85 172 25 PEBA 10.13-st translucent 1.83 175 26 PEBA 10.13-st translucent 1.9 164 27 PEBA 10.9 translucent 1.86 179 28 PEBA 10.9 translucent 1.86 177 29 PEBA 10.9 translucent 1.87 172 30 PEBA 10.9 translucent 1.89 168 31 PEBA 10.9 translucent 1.76 153 32 PEBA 10.9-st translucent 1.86 179 33 PEBA 10.9-st translucent 1.86 177 34 PEBA 10.9-st translucent 1.87 172 35 PEBA 10.9-st translucent 1.89 168 36 PEBA 6.13 white/opaque 1.86 195 37 PEBA 6.13 white/opaque 1.88 193 38 PEBA 6.13 white/opaque 2.19 188 39 PEBA 6.13-st white/opaque 1.86 195 40 PEBA 6.13-st white/opaque 2.19 188 48 PEBA 6.9-st milky-white 1.97 195 49 PEBA 6.9-st milky-white 1.89 203 50 PEBA 6.9-st milky-white 1.81 204 51 PEBA 7.10 milky/cloudy 1.73 199 52 PEBA 5.12 milky/cloudy 1.21 198 53 PEBA 7.12 translucent 1.6 189 54 PEBA 7.12 translucent 2.01 183 55 PEBA 7.14 translucent 1.85 173 56 PEBA 12.9-st translucent 1.93 173 57 PEBA 12.9-st translucent 1.76 151 58 PEBA 6.13-st translucent 1.79 186 59 PEBA 7.13 cloudy 1.48 170 60 PEBA 7.13 cloudy 1.84 177

(18) Commercially available PEBA based on PA 12 or PA 11 were also investigated. These are available from Evonik (Vestamid) or Arkema (PEBAX).

(19) Testing of the Polyether Block Amides Prepared

(20) Deposit Test

(21) Injection-moulded plaques measuring 60 mm80 mm2 mm were produced from the polyether block amides as test specimens. The formation of deposits was ascertained after the test specimen had been stored for a test period of 10 days in a closed vessel with water vapour saturation at 75 C. Deposits were assessed visually using a four-point scale (from 0-3, where 0=free of deposits and 3=subject to heavy deposits).

(22) For some specimens, no deposit tests were performed. In these cases, no entry is made in the following tables.

(23) Determination of Translucency

(24) The translucency of the aforementioned test specimens was ascertained visually. In this case the following evaluation was used (in decreasing order of translucency): 0=translucent ++ 1=translucent + 2=translucent 0 3=opaque/milky, translucent 0 4=opaque/milky, translucent 5=milky-white
Determination of Haze Value

(25) The haze value specifies the illumination through an article in transmitted light. The haze value is measured here by means of the 60602 mm plaques to ASTM standard D 1003 using a Konica-Minolta CM-3800d. Where the specimen was opaque/milky or even milky-white, determination of the haze value was usually dispensed with.

(26) TABLE-US-00003 TABLE 3 Test results of PEBA 6.10-650 (non-inventive) Mn of Mn of Translu- subunit subunit Deposit Haze cency Experiment Product 1 2 test value (visual) 1 PEBA 6.10 2300 650 1 4 2 PEBA 6.10 1100 650 0-1 4 3 PEBA 6.10 800 650 1 4 4 PEBA 6.10-st 2300 650 1 4 5 PEBA 6.10-st 1100 650 1-2 4 6 PEBA 6.10-st 800 650 1-2 4

(27) Despite some good deposit test results, the specimens of PEBA 6.10 exhibit insufficiently low translucency.

(28) TABLE-US-00004 TABLE 4 Test results of PEBA 6.13-650 (according to the invention) Mn of Mn of Translu- subunit subunit Deposit Haze cency Experiment Product 1 2 test value (visual) 7 PEBA 6.13 2300 650 0 60.1 2 8 PEBA 6.13 1100 650 0-1 33.8 1 9 PEBA 6.13 800 650 0-1 20.0 0 10 PEBA 6.13 600 650 0-1 5.3 0 11 PEBA 6.13-st 2300 650 0-1 56.1 2 58 PEBA 6.13-st 1509 650 0 66.0 0-1 12 PEBA 6.13-st 1100 650 0 28.3 1 13 PEBA 6.13-st 300 650 0-1 15.3 0 14 PEBA 6.13-st 600 650 1-2 5.8 0

(29) PEBA 6.13 satisfies both the deposit test and the requirements on translucency.

(30) TABLE-US-00005 TABLE 5 Test results of PEBA 10.10-650 and 7.13-650 (non-inventive) Mn of Mn of Translu- subunit subunit Deposit Haze cency Experiment Product 1 2 test value (visual) 15 PEBA 10.10 2268 650 0-1 3 16 PEBA 10.10 1083 650 1-2 3 17 PEBA 10.10 780 650 2-3 3 59 PEBA 7.13 1509 650 0 3 60 PEBA 7.13 600 650 2 2

(31) The test specimens of PEBA 10.10 and PEBA 7.13 are opaque/milky with low translucency or (Example 60) have a certain transparency with increased deposits.

(32) TABLE-US-00006 TABLE 6 Test results of PEBA 10.13-650 (non-inventive) Mn of Mn of Translu- Experi- subunit subunit Deposit Haze cency ment Product 1 2 test value (visual) 19 PEBA 10.13 4096 650 2 63.3 2 20 PEBA 10.13 2263 650 2 49.1 1 21 PEBA 10.13 1509 650 2 23.4 0 22 PEBA 10.13 1068 650 2 16.5 0 23 PEBA 10.13-st 4096 650 2 61.3 1 24 PEBA 10.13-st 2268 650 2 37.7 2 25 PEBA 10.13-st 1509 650 2 22.4 1 26 PEBA 10.13-st 1063 650 2 17.0 0

(33) Although both the non-stabilized and the stabilized PEBA 10.13 do exhibit a moderate to good translucency, these specimens do not pass the deposit test.

(34) TABLE-US-00007 TABLE 7 Test results of PEBA 10.9-650 (according to the invention) Mn of Mn of Translu- subunit subunit Deposit Haze cency Experiment Product 1 2 test value (visual) 27 PEBA 10.9 4096 650 0-1 80.2 2 28 PEBA 10.9 2263 650 1 60.2 1 29 PEBA 10.9 1509 650 0 41.1 0 30 PEBA 10.9 1068 650 0 30.8 0 31 PEBA 10.9 600 650 0 22.3 0 33 PEBA 10.9-st 4096 650 1 71.4 0 33 PEBA 10.9-st 2268 650 0-1 71.7 2 34 PEBA 10.9-st 1509 650 0 39.2 1 35 PEBA 10.9-st 1068 650 0 25.9 0

(35) PEBA 10.9 exhibits few to no deposits whatsoever and a good to moderate translucency.

(36) TABLE-US-00008 TABLE 8 Test results of PEBA 6.13-1000 (non-inventive) Mn of Mn of Translu- subunit subunit Deposit Haze cency Experiment Product 1 2 test value (visual) 36 PEBA 6.13 4000 1000 101 5 37 PEBA 6.13 2300 1000 102 5 38 PEBA 6.13 1100 1000 102 5 39 PEBA 6.13-st 4000 1000 101 5 40 PEBA 6.13-st 1100 1000 102 5

(37) PEBA 6.13, having a polyether subunit the molar mass of which is 1000, leads to milky-white test specimens. In contrast, PEBA 6.13 specimens having a polyether subunit of 650 g/mol exhibit moderate to good translucency (Experiments 7 to 14).

(38) TABLE-US-00009 TABLE 9 Test results using commercially available PEBA Deposit Translucency Experiment Product test (visual) 41 Vestamid E55-S3 1-2 4 42 Vestamid E62-S3 1-2 4 43 Vestamid E40-S3 1-2 4 44 Vestamid E26-S3 2-3 1 45 PEBAX Rnew 55R53 1-2 1 46 PEBAX 6333 1-2 4 47 PEBAX C 1-2 4

(39) The deposit test shows a moderate result for commercially available PEBA based on PA 11 or PA 12. The translucency in most cases turns out to be very low.

(40) TABLE-US-00010 TABLE 10 Test results of PEBA 6.9-650, PEBA 7.10-650 and 5.12-650 (non-inventive) Mn of Mn of Translu- subunit subunit Deposit Haze cency Experiment Product 1 2 test value (visual) 48 PEBA 6.9-st 1509 650 0 100.7 5 49 PEBA 6.9-st 1083 650 0 101.7 5 50 PEBA 6.9-st 600 650 0-1 102 5 51 PEBA 7.10 1509 650 0 3 52 PEBA 5.12 1760 650 3 4

(41) Specimens containing PEBA 6.9, PEBA 7.10 and 5.12 exhibit opaque/milky to milky-white test specimens.

(42) TABLE-US-00011 TABLE 11 Test results of 7.12-650, 14-650 and 12.9-650 (according to the invention) Mn of Mn of Translu- Experi- subunit subunit Deposit Haze cency ment Product 1 2 test value (visual) 53 PEBA 7.12 1509 650 1 0-1 54 PEBA 7.12 600 650 1 0-1 55 PEBA 7.14 1509 650 1 0-1 56 PEBA 12.9-st 1083 650 0 49.0 0-1 57 PEBA 12.9-st 600 650 0 39.0 0-1

(43) Test specimens containing PEBA 7.12, 7.14 or 12.9 exhibit few to no deposits and high transparency.