Polyamides based on aminoalkylpiperazine or aminoarylpiperazine for hot-melt adhesives

Abstract

A semi-crystalline polyamide including at least one monomer resulting from the condensation of a diacid and of a diamine of formula AP.Y, the semi-crystalline polyamide having the following general formula (I): AP.Y/(A)m/(Pip.Y)n/(B.Y)q and the semi-crystalline polyamide having an Mp1 less than or equal to approximately 150 C., in particular less than or equal to approximately 130 C., in particular less than or equal to approximately 120 C. and/or a Tg less than or equal to approximately 60 C., in particular less than or equal to approximately 50 C., in particular less than or equal to approximately 40 C., as determined respectively by DSC according to standard ISO 11357-3 (2013) and ISO 11357-2 (2013).

Claims

1. A semicrystalline polyamide comprising at least one monomer resulting from the condensation of a diacid and a diamine of formula AP.Y, wherein: AP represents at least one asymmetric diamine monomer of the piperazine type with the following formula: ##STR00003## wherein: R.sub.1 represents H or Z.sub.1NH.sub.2 and Z.sub.1 represents an alkyl, a cycloalkyl or an aryl having up to 15 carbon atoms, R.sub.2 represents H or Z.sub.2NH.sub.2 and Z.sub.2 represents an alkyl, a cycloalkyl or an aryl having up to 15 carbon atoms, R.sub.1 and R.sub.2 being different from one another, and Y represents at least one dicarboxylic acid excluding the dimers and/or trimers of fatty acids, said semicrystalline polyamide having the following general formula (IV):
AP.Y/Pip.Y wherein: A represents at least one polyamide with a long-chain aliphatic unit, excluding PA6, Pip denotes piperazine and Y represents at least one dicarboxylic acid excluding the dimers and/or trimers of fatty acids, and Y and Y may be identical or different, Y represents at least one dicarboxylic acid excluding the dimers and/or trimers of fatty acids, and Y may be identical to or different from Y and/or Y and said semicrystalline polyamide has a Tm.sub.1 less than or equal to about 150 C., and/or a Tg less than or equal to about 40 C., as determined by DSC according to standard ISO 11357-3 (2013) and ISO 11357-2 (2013), respectively, and a solubility in an alcohol-water mixture, in particular an isopropanol-water mixture (85/15: v/v) at room temperature (20 C.) of at least 15%, and the AP.Y/Pip.Y weight ratio is from 40/60 to 99/1.

2. The semicrystalline polyamide according to claim 1, wherein AP represents aminoethylpiperazine (AEP) and Y=Y is selected from adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexanedioic acid and octadecanedioic acid.

3. The semicrystalline polyamide according to claim 1, wherein said polyamide is selected from AEP.10/Pip.10 and AEP 12/Pip.12.

4. The semicrystalline polyamide according to claim 1, said polyamide having a Tm.sub.1 less than or equal to about 100 C. and/or a Tg less than or equal to about 35 C.

5. The semicrystalline polyamide according to claim 1, wherein the Y/Y molar ratio is from 15/85 to 85/15.

6. The semicrystalline polyimide according to claim 1, wherein AP represents aminoethylpiperazine (AEP) and Y and Y are selected from adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexanedioic acid and octadecanedioic acid.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows the DSC thermogram obtained with a copolyamide of the prior art of the platamide type (6/6.6/11/12 with respective proportions by weight 30/20/20/30). From bottom to top, first heating curve, second heating curve and cooling curve.

(2) Tg: 36.9 C. and Tm.sub.1=102.5 C. (first heating), no Tm.sub.2 in second heating, non-crystalline product.

(3) FIG. 2 shows the DSC thermogram obtained with a copolyamide of the invention (AEP.12/12: 65/35 by weight). From bottom to top, first heating curve, second heating curve and cooling curve.

(4) Tg: 18.3 C. and Tm.sub.1=91.7 C. (first heating), Tm.sub.2=93.2 C. (second heating), Tc=58.8 C., crystalline product.

(5) FIG. 3 shows the DSC thermogram obtained with a copolyamide of the invention (AEP.12/12: 70/30 by weight). From bottom to top, first heating curve, second heating curve and cooling curve.

(6) Tg: 18.7 C. and Tm.sub.1=85.5 C. (first heating), Tm.sub.2=88.3 C. (second heating), Tc=69.6 C., crystalline product.

(7) FIG. 4 shows the DSC thermogram obtained with a copolyamide of the invention (AEP.12/11/12: 60/20/20 by weight). From bottom to top, first heating curve, second heating curve and cooling curve.

(8) Tg: 18.6 C. and Tm.sub.1=89.2 C. (first heating), Tm.sub.2=89.9 C. (second heating), Tc=67.3 C., crystalline product.

(9) FIG. 5 shows the melting points and the MVRs of different copolyamides of the invention, without caprolactam, compared to those obtained with copolyamides comprising caprolactam.

(10) It shows, from left to right, the copolyamides of the invention without caprolactam: AEP.12/12 (70/30 by weight), AEP.12/12 (65/35 by weight), and the copolyamides of the prior art with caprolactam: 6/6.6/11/12 (respective proportions by weight 30/20/20/30), 6/Pip.12/12 (respective proportions by weight 30/20/50), and 6/6.6/12 (respective proportions by weight 35/20/45).

(11) This figure shows that the copolyamides of the invention without caprolactam, compared to the copolyamides with caprolactam, display a lowering of the melting point, a property that is important for adherence when gluing to fabric.

(12) The MVR (melting volume rate, which corresponds to the melt flow index) of the polyamides of the invention is determined according to standard ISO 1133-2 (2011).

EXAMPLES

Example 1: Preparation of the Polyamides of the Invention

(13) The polyamides of the invention are prepared according to the techniques known by a person skilled in the art, for example, for synthesis of AEP.10/Pip.10 40/60, which is representative of all the syntheses of the invention:

(14) A glass reactor, equipped with a stirrer of the anchor type, is charged with 10.75 g of piperazine, 9.36 g of N-aminoethylpiperazine and 39.89 g of sebacic acid. The mixture is inerted by vacuuming and then by introducing nitrogen 4 times in succession. Then the reaction mixture is heated under a nitrogen stream. When the material temperature reaches 180 C., the stirring is switched on. One hour after the material temperature reaches 250 C., vacuum (below 100 mbar) is applied. The medium become viscous and synthesis is stopped until the desired stirring torque is reached.

(15) The product obtained is yellow and translucent.

(16) The melting points Tm.sub.1, and Tm.sub.2, glass transition temperature (Tg), enthalpy and crystallization temperature (Tc) are measured by DSC (differential scanning calorimetry) in accordance with standard ISO 11357-2 (2013) and standard ISO 11357-3 (2013), according to the following protocol:

(17) 1: Equilibrate at 20.00 C.

(18) 2: Cool at a rate of 10.00 C./min to 50.00 C.

(19) 3: Maintain this temperature for 5.00 min

(20) 4: Heat at a rate of 20.00 C./min to 250.00 C.

(21) 5: Maintain this temperature for 5.00 min

(22) 6: Cool at a rate of 10.00 C./min to 50.00 C.

(23) 7: Maintain this temperature for 5.00 min

(24) 8: Heat at a rate of 20.00 C./rain to 250.00 C.

(25) Various polyamides were prepared, with the characteristics detailed below, and notably the following polyamides: AEP.Y/A, AEP and notably the following polyamides: AEP.Y, AEP.Y/A, AEP.Y/6.Y, AEP.YPip.Y and AEP.Y/AEP.Y/Pip.Y/Pip.Y.

(26) All the products obtained have an intrinsic viscosity above 0.4 as determined according to ISO 307 but changing the solvent (use of m-cresol in place of sulphuric acid and the temperature being 20 C.).

Example 2: AEP.Y and AEP.Y/A (Y=6, 9, 10, 12 and a Represents A, A=11 or 12)

(27) The percentages of each monomer are stated by weight.

(28) TABLE-US-00001 enthalpies Description Tm.sub.1 Tg Tm.sub.2 Tc (J/g) AEP.6/12 20/80 154.9 30 145.9 71.8 36 40/60 128.7 26 121.3 88 3 60/40 102 33 80/20 115 44 100/0 145 54 AEP.9/12 20/80 151.5 27 152.5 96.6 43 40/60 131.8 19 129.3 50.6 27 60/40 99.9 21 80/20 87 25 100/0 115 32 AEP.10/12 20/80 160.2 27 156.4 106.9 50 40/60 137.7 20 126 37.2 29 60/40 104.1 20 80/20 98.4 24 100/0 121 30 AEP.12/12 20/80 160.9 29 158.3 113.1 48 40/60 137.5 24 136.7 68.4 37 50/50 117.2 24 115.8 46 24 60/40 105.2 20 99.2 52 21 65/35 96.5 21 96.2 66 14 70/30 82.3 21 90.8 72 2 80/20 82 17 100/0 120.2 19 AEP.6/11 20/80 159.4 32 158.5 109.7 46 40/60 132 27 122.9 80 27 60/40 100.7 34 80/20 140 44 100/0 145 57 AEP.9/11 20/80 164.5 30 162.3 120 53 40/60 132.7 20 130.3 47.8 35 60/40 96.9 22 80/20 55 25 100/0 115 32 AEP.10/11 20/80 164.9 29 161.7 116.3 49 40/60 135.6 26 127.7 47.9 28 60/40 89 22 80/20 59 26 100/0 121 30 AEP.12/11 20/80 172.9 30 167.5 127.3 50 40/60 146.6 25 140.8 73.4 35 60/40 108.5 21 102.1 69 11 80/20 90.6 18 100/0 120.2 19

Example 3: AEP.Y/A (Y=12 and A Represents A, A=11 and 12)

(29) The percentages of each monomer are stated by weight

(30) TABLE-US-00002 enthalpies Description Tm.sub.1 Tg Tm.sub.2 Tc (J/g) AEP.12/11/12 60/20/20 89 19 90 67 8

Example 4: AEP.Y/Cx.Y (Y=6, 10, 12 and 14, Cx=6)

(31) The percentages of each monomer are stated by weight

(32) TABLE-US-00003 enthalpies Description Tm.sub.1 Tg Tm.sub.2 Tc (J/g) AEP.6/6.6 256.3 48 255.3 229 85 (0/100) AEP.6/6.6 236.6 51 233.6 190 57 (20/80) AEP.6/6.6 207 51 203.1 135 44 (40/60) AEP.6/6.6 161.4 50 (60/40) AEP.6/6.6 137.4 51 (80/20) AEP.10/6.10 118 30 (80/20) AEP.10/6.10 160 30 155.3 92 27 (60/40) AEP.10/6.10 185 35 181.2 105 41 (40/60) AEP.10/6.10 206 34 204.9 159 75 (20/80) PA 6.10 222 31 218.5 186 108 AEP.12/6.12 216.4 37 214.1 189 106 (0/100) AEP.12/6.12 200.7 24 197.4 168 80 (20/80) AEP.12/6.12 187.1 15 183.6 151 79 (40/60) AEP.12/6.12 165.8 16 161.4 117 56 (60/40) AEP.12/6.12 129.6 24 (80/20) AEP.14/6.14 211.1 38 208.9 188 96 (0/100) AEP.14/6.14 189.3 29 186.7 151 70 (20/80) AEP.14/6.14 179.4 25 176.7 144 72 (40/60) AEP.14/6.14 158.5 23 154.6 94 44 (60/40) AEP.14/6.14 130.2 15 127.8 28 35 (80/20) AEP.14/6.14 121.9 18 119.4 26 28 (100/0)

Example 5: AEP.Y/Pip.Y (Y=10 and 12)

(33) The percentages of each monomer are stated by weight

(34) TABLE-US-00004 enthalpies Description Tm.sub.1 Tg Tm.sub.2 Tc (J/g) AEP.12/PIP.12 (15/85) 134 28 136.9 76 33 AEP.12/PIP.12 (30/70) 115 24 117.9 51 28 AEP.12/PIP.12 (35/65) 108 20 107.2 49 27 AEP.12/PIP.12 (40/60) 97 26 104.6 82 5 AEP.12/PIP.12 (50/50) 85 24 AEP.12/PIP.12 (60/40) 55 24 AEP.12/PIP.12 (80/20) 98 24 Pip.10/AEP.10 (wt % 20/80) 111 29 Pip.10/AEP.10 (wt %: 40/60) 29 Pip.10/AEP.10 (wt %: 50/50) 100 30 Pip.10/AEP.10 (wt %: 60/40) 119 28 Pip.10/AEP.10 (wt %: 70/30) 132 32 Pip.10/AEP.10 (wt %: 85/15) 158 32 99 158 44.5 Pip.10/AEP.6 (wt %: 70/30) 149 40 88 149 14

Example 6: AEP.Y/AEP.Y/Pip.Y/Pip.Y with and without B.Y/B.Y (Y=10 and Y=12)

(35) The proportions of each monomer are stated in moles.

(36) TABLE-US-00005 Molar composition AEP 35 35 35 35 35 35 35 20 35 20 35 35 35 35 30 30 Pip 65 65 65 65 65 65 65 65 65 65 65 65 65 65 70 70 Jeffamine 15 15 EDR148 DC10 100 80 60 40 20 30 20 25 30 35 22 21 77 22 77 DC12 20 40 60 80 100 70 80 85 70 75 82 81 27 82 27 PEG 600 10 10 4 2 4 4 4 Tm1 123 104 82 84 91 108 78 91 83 82 89 91 91 103 97 109 Tg 25 23 21 21 18 20 26 17 2 16 1 9 17 10 12 9 Tm2 88.1 107.2 92 82 87 73 89 91 97 114 Tc 61 49 72 34 74 32 45 63 40 80 Enthalpy 17 27 9 16 2 17 19 13 21 2 (J/g)

Example 7: Test of Adherence of the Copolyamides of the Invention and of Resistance to Washing

(37) Laminator: Model HP-450M,MS Pressure: 1.0 kg/cm.sup.2 gluing time: 25 s Peeling machine: Hongda Tensometer Peeling test at 150 mm/min Number of washing cycles: 2

(38) The various heat-sensitive adhesives are submitted to two machine washings at 60 C. for 1.5 h for each washing and then to drying. Types of textiles: Cotton (90% cotton, 10% polyester)

(39) The sample of cotton is 150 mm long and 50 mm wide.

(40) The copolyamide film to be glued to the sample measures 40 m in thickness. The results are presented in the following table.

(41) TABLE-US-00006 Retention of the Initial properties of Melting adhesive adherence after point Heat-sealing force 2 washings and Copolyamide ( C.) temperature (N/cm) then drying (%) 6/6.6/11/12 102 160 C. 5.8 58% (30/20/20/30 by weight) AEP.12/12 92 180 C. 5.4 66% (65/35 by weight) AEP.12/12 85 180 C. 4.0 65% (70/30 by weight)