COPOLYAMIDES WITH ALTERNATING REPEAT UNITS
20170298181 · 2017-10-19
Inventors
Cpc classification
C08L2205/025
CHEMISTRY; METALLURGY
C08G69/26
CHEMISTRY; METALLURGY
International classification
C08G69/26
CHEMISTRY; METALLURGY
Abstract
The invention relates to a process for the preparation of a PA XY/XZ polyamide, more particular a copolyamide having alternating XY units and XZ units and a process for the manufacture thereof. Further, the present invention relates to compositions and articles comprising said copolyamide. Furthermore, the present invention relates to diamines and salts which are intermediary products of the process for the manufacture of said copolyamide.
Claims
1. Process for the manufacture of a PA XY/XZ copolyamide having alternating units XY and XZ of a first polyamide PA XY and a second polyamide PA XZ comprising: a) reacting a diamine X and a dicarboxylic acid or a derivative thereof Y thereby making a XYX diamine; b) reacting the XYX diamine with a dicarboxylic acid or a derivative thereof Z thereby making a salt XYX,Z thereof; c) solid state polymerizing the salt XYX,Z obtained in b) at a temperature of at least 5° C. below the melting point of the salt XYX,Z obtained after step b) as measured by DSC at a heating rate of 10° C./min according to standard ISO 11357-3 (2009), wherein PA XY is a semi-crystalline semi-aromatic polyamide or an aliphatic polyamide obtained from a C2 to C36 dicarboxylic acid and a C2 to C36 diamine; PA XZ is a semi-crystalline semi-aromatic polyamide or an aliphatic polyamide obtained from a C2 to C36 dicarboxylic acid and a C2 to C36 diamine, and Y and Z are different dicarboxylic acids or derivatives thereof.
2. Process according to claim 1, wherein Y is an aromatic dicarboxylic acid or a cyclic aliphatic dicarboxylic acid.
3. Process according to claim 1, wherein Y is terephthalic acid, 4,4′-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid, or a derivative thereof.
4. Process according to claim 1, wherein Z is an aliphatic dicarboxylic acid or derivative thereof comprising at least 6 carbon atoms.
5. Process according to claim 1, wherein X is a linear aliphatic diamine selected from the group consisting of C2 to C18 diamines.
6. Process according to claim 5, wherein X is a linear aliphatic diamine comprising an even number of carbon atoms.
7. Process according to claim 5, wherein X is selected from the group consisting of 1,4-diaminobutane, 1,6-diaminohexane, 1,10-diaminodecane, 1, 12-diaminododecane and 1,18-diaminooctadecane.
8. PA XY/XZ copolyamide having alternating XY and YZ units obtainable by the process as defined in claim 1, wherein the copolyamide has a degree of randomness R of at least 1.5 as determined by the integral ratio of the middle C atoms in the diamine .sup.13C-NMR as calculated from the probability distribution according to Devaux et al., J. Pol. Sci.: Pol. Phys. 20, 1875-1880 (1982).
9. PA XY/XZ copolyamide having alternating XY and YZ units obtainable by the process as defined in claim 1, wherein the copolyamide has a melting temperature in the range of at least 5° C. above the melting point of the statistical copolymer.
10. Polyamide composition comprising: the PA XY/XZ copolyamide having alternating units XY and XZ obtainable by the process according to claim 1; and at least one further component.
11. Polyamide composition according to claim 10, wherein one of the at least one further component is a further polyamide and wherein the composition is a blend of PA XY/XZ copolyamide having alternating units XY and XZ and the further polyamide.
12. Polyamide composition according to claim 10, wherein the PA XY/XZ copolyamide is processed with a further polyamide by a process selected from the group consisting of melt processing, solution processing and solid state processing.
13. Articles comprising the PA XY/XZ copolyamide according to claim 1.
Description
EXAMPLES
Materials
[0043] The materials 1,4 diaminobutane (DAB), hexamethylenediamien (HMDA), bis(2-ethylhexyl)terephthalate, dimethylterephthalate (DMT), adipic acid, sebacic acid and potassiumtriflouroacetate were obtained from Acros. Hydrogenated Dimerized fatty acid was obtained as Pripol 1009 from Croda. 1,18-Octadecanedioic acid was obtained from Emerox (Emerox 118). DMSO, DMF, sodiumethoxide, acetone, hexafluoropropanol and ethanol (96%) were obtained from Acros. All chemicals were used as received.
[0044] Analysis Techniques
[0045] 1H-NMR and 13C NMR spectra were taken with a Bruker 500 MHz spectrometer equipped with a 5 mm cryogenic cooled probe operating at 313K. For the 13C NMR, the samples were dissolved in H2SO4 using an extra inserted 5 mm tube containing CDCl3. The CHCl3 signal was taken a reference at 7.24 ppm.
[0046] The XTX diamine purity of examples 1a, 1b and 2 was determined from .sup.1H-NMR spectroscopy as described in literature (D. Husken, R. J. Gaymans, Polymer 44 (2003) 7043-7053, eq. 1):
e represents the integral of the peak corresponding to the CH2 group next to the amide bond.
f represents the integral of the peak corresponding to the CH2 group that is coupled to the NH2 end group.
[0047] For instance, the relevant NMR data of examples 1a, 1b and 2 are presented below.
##STR00001##
[0048] XTX diamine purity is defined as (2-e/f) 100%.
[0049] For the 13C NMR the sample was dissolved in hexafluoroisopropanol (HFIP). The HFIP resonance was taken as a reference at 77 ppm. When taking HFIP as a reference peak (68.07 ppm), 1.01 ppm has to be substracted from the shift values of table 2. For determining the randomness R.
[0050] Determined from the Integrals from .sup.13C-NMR:
[0051] Randomness R in the copolyamide is determined from the following equation:
(equation as mentioned in introduction)
[0052] Where:
F.sub.BB1 is the molar fraction of monomer BB.sup.1 (or Y) of all BB monomers (Y+Z) in the copolymer.
F.sub.BB2 is the molar fraction of monomer BB.sup.2 (or Z) of all BB monomer units in the copolymer.
[0053] The relative molar contents of BB.sup.1 and BB.sup.2 a, [BB.sup.1] and [BB.sup.2] are represented by the peak integrals of the carbon atom of the representative monomer units.
[0054] For the middle two C atoms in a diamine with an even numbered linear diamine X, a copolyamide PA XY/XZ can result in four peaks in the .sup.13C-NMR spectrum.
[0055] f(BB.sup.1AABB.sup.1): is the integral of the two middle C atoms of the even numbered linear diamine X in the copolymer divided by the integral of all peaks corresponding to the middle C atoms of the even numbered linear diamine X.
[0056] f(BB.sup.1AABB.sup.1): is the integral of the two middle C atoms of the even numbered linear diamine X in the copolymer divided by the integral of all peaks corresponding to the middle C atoms of the even numbered linear diamine X.
[0057] f(BB.sup.1AABB.sup.2) is the integral of the peak corresponding the C atom closest to the diacid or diacid derivate unit in the polyamide BB1 (or Y) of the two middle C atoms of the even numbered linear diamine X in the copolymer divided by the integral of all four peaks corresponding to the middle C atoms of the even numbered linear diamine X ((BB.sup.1AABB.sup.1)+(BB.sup.1AABB.sup.2)+(BB.sup.2AABB.sup.1)+(BB.sup.2AABB.sup.2)).
[0058] f(BB.sup.2AABB.sup.1) is the integral of the peak corresponding the middle the C atom closest to the diacid or diacid derivative unit in the polyamide BB2 (or Z) of the two middle C atoms of the even number linear diamine X in the copolymer divided by the integral of all four peaks corresponding to the middle C atoms of the even numbered linear diamine X.
[0059] For odd numbered linear diamines X, there are three peaks, because the peak corresponding to (BB.sup.1AABB.sup.2) also corresponds to (BB.sup.2AABB.sup.1) and correspond to the middle C atom in the odd numbered linear diamines X. In this case f(BB.sup.1AABB.sup.2)=f(BB.sup.2AABB.sup.1) is 0.5 times the integral of the middle C atom of the odd numbered linear diamine X in the copolymer divided by the integral of all three peaks corresponding to the middle C atoms of the odd numbered linear diamine X ((BB.sup.1AABB.sup.1)+(BB.sup.1AABB.sup.2)+(BB.sup.2AABB.sup.1)+(BB.sup.2AABB.sup.2)).
[0060] Size Exclusion Chromatography measurement has been performed on Viscotek GPCMax VE2001 solvent/sample module system, equipped with TDA302 triple detector array. For chromatographic separation 3 PFG linear XL columns from PSS have been used. Detectors and columns were operated at 35° C. Prior Size Exclusion Chromatography polymer was dissolved in hexafluoroisopropanol/0.1% potassiumtriflouroacetate which was also used as an eluent in SEC at a flow rate of 0.8 ml/min. The molar mass has been determined with triple detection method, using the refractive index, differential viscosity and light scattering signals. For the calculation, a do/dc of 0.30 ml/g was used.
[0061] DSC is measured at a heating rate of 10° C./min according to standard ISO 11357-3 (2009). The peak half with of the melting point of the polymer is determined by measuring the with of the peak in ° C. at half the height of the peak height from the base line.
Preparation of Diamine XYX
Example 1a (EX 1a): Preparation of di-(4-aminobutyl)terephthalamide (4T4 diamine)
[0062] A flask was charged with 30 g bis(2-ethylhexyl)terephthalate, and 80 g 1,4-diaminobutane, and heated to 50° C. after which the sodium ethoxide (4 g) was added. After 17 hrs the reaction mixtures was cooled to room temperature after which 0.7 mL demineralized water was added to quench the catalyst. The resulting mixture was precipitated in acetone (1 L) filtered and the solid was washed with acetone. The crude material (14.6 g) was recrystallized from N,N-dimethylformamide (DMF, 600 mL), after which the solid was washed twice with DMF (2×50 mL) and twice with acetone (2×100 mL) and dried with a small stream of nitrogen in a 50 mbar vacuum at 50° C., resulting in a pure solid white 4T4. The bis(2-ethylhexyl)terephthalate conversion was 95% according to .sup.1H-NMR. The diamine had a DSC melting peak at 203° C., recorded at 20 K/min.
Example 1b (EX 1b): Preparation of di-(4-aminobutyl)terephthalamide (4T4 diamine)
[0063] A mixture of dimethylterephthalate (DMT) (195 g, 1.0 mol) and DAB (880 g, 10 mol) was heated to 95° C. in a 3 liter stirred round bottomed flask with nitrogen inlet and a reflux condenser. Formed methanol was removed by distillation. After 8 h at 95° C. the thick suspension was filtered. Then the filter cake was stirred with 500 ml toluene at 85° C. The product was collected by filtration and three times washed with each time 60 ml hot toluene (85° C.). Finally the product was washed twice with each time 150 ml of ethanol (96%). and dried with a small stream of nitrogen in a 50 mbar vacuum at 50° C. The product was recrystallised in 3 portions by each time adding 5 liter n-butylacetate to 100 g of the product and refluxing at atmospheric pressure for 10 minutes and slow cooling to room temperature and filtering. The collected product was dried with a small stream of nitrogen in a 50 mbar vacuum at 50° C. total yield of 4T4 diamine was 228 g.
Example 2 (EX 2): preparation of di-(6-aminohexyl)terephthalamide (6T6 diamine)
[0064] 379 grams of 1,6-hexamethylenediamine and 78.1 grams of dimethylterephthalate were heated to 80° C. under a nitrogen atmosphere and stirred at 80° C. for 6 hours. The suspension was cooled to room temperature and 1 L of THF was added. The mixture was stirred for 30 minutes and filtrated. The product was recrystallized from 1,4-dioxane to yield the 6T6 diamine as a white crystalline powder (41% yield).
Preparation of salt of XYX,Z
Example 3 (EX3): Preparation of 4T4,6 Salt
[0065] 20 ml of ethanol (96%) and 5 ml of DMSO was added to a 100 ml round bottom flask charged with 0.218 g 4T4 diamine of example 1 a. The mixture was stirred and heated under reflux until the solid had dissolved. 0.103 g Adipic acid was dissolved in 10 ml of ethanol (96%) at room temperature. Solutions were combined and after mixing allowed to cool to room temperature. Cream white precipitate filtered and washed with ethanol and dried with a small stream of nitrogen in a 50 mbar vacuum at 50° C.
Example 4 (EX 4): Preparation of 4T4,10 Salt
[0066] 20 ml of ethanol (96%) and 5 ml of DMSO was added to a 100 ml round bottom flask charged with 0.218 g 4T4 diamine of example 1a. The mixture was stirred and heated under reflux until the solid had dissolved. 0.144 g Sebacic acid was dissolved in 10 ml of ethanol (96%) at room temperature. Solutions were combined and after mixing allowed to cool to room temperature. Cream white precipitate filtered and washed with ethanol and dried with a small stream of nitrogen in a 50 mbar vacuum at 50° C.
Example 5a (EX 5a): Preparation of 4T4,18 Salt
[0067] 45 ml of ethanol (96%) and 15 ml of DMSO was added to a 100 ml round bottom flask charged with 0.202 g 4T4 diamine of example 1a. The mixture was heated under reflux until it dissolved. 0.226 g 1,18-octadecanedioic acid was dissolved under reflux at 95° C. in 10 ml of ethanol (96%). The dissolved dicarboxylic acid was added to the 4T4 diamine solution and the combined solution was mixed for 2 hours while refluxing and then cooled to room temperature. A cream white precipitate was filtered and washed with ethanol and dried with a small stream of nitrogen in a 50 mbar vacuum at 50° C.
Example 5b (EX 5b): Preparation of 4T4,18 Salt
[0068] 8 liter of ethanol (96%) and 8 liter of DMSO were mixed with 202 g 4T4 diamine of example 1 b. The mixture was heated in a mixed pressure vessel at 120° C. for 30 min hour. 256 g 1,18-octadecanedioic acid melted and added as a melt to the 4T4 diamine solution into reactor while mixing. The mix was cooled to room temperature and filtered, washed with ethanol and dried with a small stream of nitrogen in a 50 mbar vacuum at 50° C. Yield: 450 g of 4T4 18 salt.
Example 6 (EX 6): Preparation of 4T4,36 Salt
[0069] 50 ml of ethanol (96%) and 5 ml of DMSO was added to a 100 ml round bottom flask charged with 0.206 g 4T4 diamine of example 1a. The mixture was heated stirred under reflux for 1 hours. 0.42 g Pripol 1009 was dissolved in 4 ml of ethanol (96%) at room temperature. This solution was added to the 4T4 solution, which was then removed from the heat to cool, whilst stirring. White precipitate was filtered and collected and dried with a small stream of nitrogen in a 50 mbar vacuum at 50° C.
Example 7 (EX 7): Preparation of 6T6,6 Salt
[0070] 10 ml of ethanol (96%) and 8 ml of DMSO was added to a 100 ml round bottom flask charged with 0.237 g 6T6 diamine. The mixture was stirred and heated under reflux for 15 minutes. 0.102 g Adipic acid was dissolved in 10 ml of ethanol (96%) at room temperature. Solutions were combined and after mixing allowed to cool too room temperature. The white precipitate was filtered and washed with ethanol and dried at room temperature in the fume hood until constant weight by the stream of air passing. Yield was 0.265 g
Example 8 (EX 8): Preparation of 6T6,10 Salt
[0071] 10 ml of ethanol (96%) and 8 ml of DMSO was added to a 100 ml round bottom flask charged with 0.237 g 6T6 diamine. The mixture was stirred and heated under reflux for 15 minutes. 0.142 g sebacic acid was dissolved in 10 ml of ethanol (96%) at room temperature. Solutions were combined and after mixing allowed to cool too room temperature. The white precipitate was filtered and washed with ethanol and dried at room temperature in the fume hood until constant weight by the stream of air passing. Yield was 0.286 g
Example 9 (EX 9): Preparation of 6T6,18 Salt
[0072] 10 ml of ethanol (96%) and 8 ml of DMSO was added to a 100 ml round bottom flask charged with 0.237 g 6T6 diamine. The mixture was stirred and heated under reflux for 15 minutes. 0.220 g 1,18-octadecanedioic acid was dissolved in 10 ml of ethanol (96%) at 80° C. Solutions were combined and after mixing allowed to cool too room temperature. The white precipitate was filtered and washed with ethanol and dried at room temperature in the fume hood until constant weight by the stream of air passing. Yield was 0.370 g.
Solid State Polymerization into the Copolymer with Alternating Units
Example 10 (EX 10): Polymerization of 4T4,10 Salt into Alternating PA 4T/410 Copolymer
[0073] 4T4,10 salt (8.442 mg) was weighed into an aluminum 0.04 ml crucible and closed with an aluminium lid perforated with a 0.05 mm hole. Sample was heated in a TGA instrument from 25° C. to 120° C. at a heating rate of 10 K/min and was held at 120° C. for 5 minutes. The sample was then heated to 190° C. at 10 K/min and held at 190° C. for 300 minutes. This was done under an atmosphere of N.sub.2 at 50 ml/min. Over the whole process, 8.19% mass loss was recorded, 6.23% mass loss occurred whilst the sample was at 190° C.
Example 11 a (EX 11a): Polymerization of 4T4,18 Salt into Alternating PA4T/418 Copolymer
[0074] 4T4,18 salt (7.654 mg) of example 5a was weighed into an aluminum 0.04 ml crucible and closed with an aluminium lid perforated with a 0.05 mm hole. Sample was heated in a TGA machine from 25° C. to 120° C. at 10 K/min and was held at 120° C. for 5 minutes. Sample was then heated to 190° C. at 10 K/min and held at 190° C. for 300 minutes. This was done under an atmosphere of N.sub.2 at 50 ml/min. Over the whole process, 6.62% mass loss was recorded, 5.81% mass loss occurred whilst sample was at 190° C.
Example 11 b (EX 11 b): Polymerization of 4T4,18 Salt into Alternating PA4T/418 Copolymer
[0075] 4T4,18 salt (350 g) of example 5b was weighed into a rotavap, equipped with a 2 liter flask and inertized by evacuation and filling with nitrogen. The flask was heated with an oil bath to 190° C. and kept at that temperature for 6 hours, allowing the water to be distilled off. Then content was cooled under a nitrogen stream, yielding 322 g of the PA 4T4,18 polyamide. With a melting point of 309°.
Example 12 (EX 12): Polymerization of 4T4,36 Salt into Alternating PA4T4/36 Copolymer
[0076] 4T4.36 salt (8.442 mg) was weighed into an aluminum 0.04 ml crucible and closed with an aluminium lid perforated with a 0.05 mm hole. Sample was heated in a TGA instrument from 25° C. to 120° C. at 10 K/min and was held at 120° C. for 5 minutes. Sample was then heated to 190° C. at 10 K/min and held at 190° C. for 300 minutes. This was done under an atmosphere of N.sub.2 at 50 ml/min. Over the whole process, 4.15% mass loss was recorded, 4.01% mass loss occurred whilst sample was at 190° C.
Example 13 (EX 13): Polymerization of PA 6T6,6 Salt into PA6T6,6 Copolymer
[0077] This was prepared as example 10, starting with 9.85 mg of 6T6,6 salt and reacting it for 600 minutes at 200° C. DSC melting point 313° C.
Example 14 (EX 14): Polymerization of PA 6T6,10 Salt into Alternating PA6T6/10 Copolymer
[0078] This was prepared as example 10, starting with 9.95 mg of 6T6,10 salt and reacting it for 600 minutes. The observed mass loss at 190° C. was 6.1 wt. %. and DSC melting point 283° C.
Example 15 (EX 15): Polymerization of PA 6T6,18 Salt into Alternating PA6T6/18 Copolymer
[0079] This was prepared as example 10, starting with 6.01 mg of 6T6,18 salt and reacting it for 600 minutes at 200° C. The observed mass loss was 5.6 wt. %. and DSC melting point 252° C.
Comparative Examples
Comparative Example 1 (CE 1): Statistical PA4T/418 (50/50 mole/mole)
[0080] PA4T/418 oligomer was prepared in a 2 liter pressure autoclave. DAB (280 g, 3.18 mole) was mixed with 490 g water and charged into the reactor, terephthalic acid (216 g, 1.3 mole) and 1,18 octadecanedioic acid (409 g, 1.3 mole) was added while stirring. The reactor was closed under inert conditions (N2). The content was heated to 200° C. in 30 min. At this temperature, 300 ml of water was removed by distilling off over 50 minutes, while keeping the pressure constant by heating the mixture. Then, the temperature was increased to 230° C. in 10 minutes and another 90 ml of water was distilled off over 20 minutes, while keeping the pressure constant by heating the mixture. Then, the temperature was increased to 250° C. in 10 minutes time and the mix was reacted for 20 minutes. The reactor content was flashed into an inertized vessel at atmospheric pressure, allowing the steam to leave the flashing vessel. The product was heated in a static bed reactor in a stream of N2 and steam in a 2 to 1 wt. ratio for 4 hours at 260° C. The product showed a low melt enthalpy of 70 J/g and an R value of 1.0 as calculated from the peak integrals of the .sup.13C-NMR spectrum.
Comparative Example (CE 2): Statistical PA6T/610 (50/50 mole/mole)
[0081] PA6T/610 was prepared in a 2 liter pressure autoclave. HMDA (217 g, 2.67 mole) and 0.5 g sodiumhypophosphitemonohydrate was dissolved into 338 g water and charged into the reactor. 217 g PTA (1.31 mole) and 267 g sebacic acid (1.31 mole) and 1.7 g benzoic acid (0.014 mole) were added while stirring. The reactor was closed and heated in 60 min to 250° C. The mix was kept at that temperature for 180 min, while keeping the pressure at 24 bar by allowing the water to evaporate. Then the reaction temperature was increased to 280° C. and the pressure was released over 60 min to atmospheric pressure by allowing the water to leave the reactor. The product melt then was released from the reactor and cooled in a water bath. The product was dried under vacuum oven at 50 mbar and 90° C. for 16 hrs. The product had a DSC melting point of 272° C. and a melt enthalpy of 35 J/g.
Comparative Example 1 (CE 3): Statistical PA 4T/46
[0082] PA4T/46 oligomer was prepared according to Gaymans et al. (Journal of Polymer Science, vol. 27, no. 2, 1989, p. 423-430) in a 0.008 liter pressure autoclave. 46 salt ((salt of equimolar amounts of DAB and adipic acid, 0.96 g, 4.1 mmole) was mixed with 4T salt (salt of equimolar amounts of DAB and terepthalic acid, 1.04 g, 4.1 mmole) and charged into the reactor. On top of the powder mix, 0.058 g DAB and 0.1 g water was added. The reactor was closed under inert conditions (N2). The content was heated to 210° C. in 60 min and kept at that temperature for 40 min. The closed reactor was then cooled to room temperature in 5 min. The product was crushed and the powder was reacted in a static bed reactor in a stream of N2 and steam in a 2 to 1 wt. ratio for 4 hours at 260° C. The product showed an R value of 0.94 as calculated from the peak integrals of the .sup.13C-NMR spectrum.
TABLE-US-00001 TABLE 1 XTX diamine 1H-NMR data and purities XTX Peak e Peak f diamine Shift* intensity Shift* Intensity elf purity Unit i ppm — ppm — — % EX 1a 2 3.67 0.985 3.08 0.912 1.08 92 EX 1b 2 3.67 0.970 3.08 0.934 1.04 96 EX 2 4 3.61 0.966 3.01 0.959 1.006 99.3 *Spectra taken from D.sub.2SO.sub.4 solution with CHCl.sub.3 as reference peak at 7.24 ppm
TABLE-US-00002 TABLE 2 13C-NMR data for the determination of R f(BB.sup.1-AA- f(BB.sup.2-AA- f(BB.sup.1-AA- f(BB.sup.1-AA- BB.sup.2) BB.sup.1) BB.sup.1) BB.sup.1) (integral) (integral) (integral) (integral) BB1 BB2 Shift Shift Shift Shift (F.sub.BB1) (F.sub.BB2) (ppm) (ppm) (ppm) (ppm) R PA4T4, 10 T 10 25.86 25.80 25.92 25.73 2.0 EX 10 (0.50) (0.50) (0.50) (0.50) (0) (0) PA4T4, 18 T 18 25.86 25.79 25.92 25.74 2.0 EX 11a (0.51) (0.49) (0.51) (0.49) (0) (0) PA4T4, 18 T 18 25.86 25.79 25.92 25.74 2.0 EX 11b (0.50) (0.50) (0.50) (0.50) (0) (0) PA4T4, 36 T 36 24.41 24.29 — — 2.0 EX 12 (0.5) (0.5) (0.5) (0.5) (0) (0) PA6T6, 10 T 10 25.84 25.78 25.88 25.75 1.8 EX 14 (0.5) (0.5) (0.45) (0.45) (0.05) (0.05) PA 4T/418 T 18 25.87 25.79 25.92 25.74 1.0 CE 1 (0.51) (0.49) (0.25) (0.25) (0.26) (0.24) PA 4T/46 T 6 25.81* 25.81* 25.92 25.71 0.94 CE 3 (0.48) (0.52) (0.23) (0.23)* (0.23) (0.29) PA 418 25.92 — (1.00) *f(BB.sup.1-AA-BB.sup.2) and f(BB.sup.2-AA-BB.sup.1) occur as one peak of total integral 0.46.
TABLE-US-00003 TABLE 3 Tm, ΔHm, peak half widths and Mn data Peak Mn half T½ Mass SEC Tm ΔHm width (min) loss (kg/ Example Copolymer (° C.) (J/g) (° C.) 190° C. (wt. %) mol) EX 10 PA 4T4, 10 318 144 6 187 7.5 EX 11a PA 4T4, 18 309 142 5 80 5.61 4.8 EX 11b PA 4T4, 18 309 EX 12 PA 4T4, 36 250 48 15 10 4.25 Not sol EX 13 PA 6T6, 6 313 152 8.5 EX 14 PA 6T6, 10 283 143 140 6.1 EX 15 PA 6T6, 18 252 116 5.5 CE 1 PA 4T/418 260 70 — 10.9 CE 2 PA6T/610 272 35 >500 (melt)
Additional Experiment: Preparation of PA418
[0083] PA418 was prepared by heating the ceramic heating mantle of a 100 ml glass reactor (equipped with a magnetic stirring rod and a reflux condenser), containing a mix of 11.46 g (0.130 mol) DAB and 39.05 g (0.124 mol) 1,18-octadecanedioic acid under a nitrogen atmosphere subsequently at 145° C. for 105 minutes, 160° C. for 60 minutes, 180° C. for 225 minutes and 250° C. for 945 minutes. The product was cooled, milled to powder and dried in a vacuum of 50 mbar for 16 hrs.