Polyesteramides, polyetheresteramides and process for preparation thereof

Abstract

Novel polyesteramides and polyetheresteramides are provided which have the formula: ##STR1## wherein A represents a divalent polyamide group, R 3 and R 4 represent hydrogen, or only one of R 3 , or R 4 is an alkyl radical containing from 1 to 24 carbon atoms, R 1 is a linear or branched, alkyl radical, or an unsaturated radical containing from 1 to 24 carbon atoms or an aromatic or cycloaliphatic radical, y+z has a value between 2 and 100, n represents a number such that the recurring units constitute a macro molecular chain. These products are obtained by polycondensation of a dicarboxylic polyamide with α, ω diol which is a hydroxylated beta-tertiary amine or a polyoxyalkyleneglycol containing in the chain one tertiary amine function.

Claims

What is claimed is: 1. Polyesteramides and polyetheresteramides of the formula ##STR33## wherein ##STR34## represents a dicarboxylic acid polyamide sequence having a medium molecular weight between 300 and 15,000; R 3 and R 4 represent hydrogen or only one of the two represents hydrogen the other one being an alkyl radical containing from 1 to 24 carbon atoms; R 1 is a linear or branched, saturated or unsaturated alkyl radical containing from 1 to 24 carbon atoms or an aromatic or cycloaliphatic radical; y+z has a value between 2 and 100, each being at least equal to 1; and n represents the number of recurrent units that constitute the macromolecular chain; and wherein the proportion by weight of the group ##STR35## represents from 2 to 90% of the total group ##STR36## wherein A, R, --R 4 , y and z are as indicated. 2. Polyesteramides and polyetheresteramides according to claim 1, wherein R 3 or R 4 represents --CH 3 . 3. Polyesteramides and polyetheresteramides according to claim 1 or 2, wherein n is between 1 and 75. 4. Polyesteramides and polyetheresteramides according to claim 1 or 2, wherein the dicarboxylic polyamide sequence ##STR37## has the formula ##STR38## wherein R 5 is a hydrocarbon chain constituting a lactam and/or an aminoacid of the structure ##STR39## wherein R 7 and R 8 are respectively the hydrocarbon residue of a diacid and of a diamine, R 6 represents the rest of an organic diacid, p and q are identical or different, and one of them can be zero, represent a repetition of a number of recurrent units that constitute the macromolecular chain of the dicarboxylic polyamide sequence. 5. Polyesteramides and polyetheresteramides according to claim 4, wherein the hydrocarbonated chain of R 5 contains from 4 to 14 carbon atoms. 6. Polyesteramides and polyetheresteramides according to claim 4 wherein R 6 is an aliphatic, cycloaliphatic or aromatic group. 7. Polyesteramides and polyetheresteramides according to claim 4, wherein the medium molecular weight of the dicarboxylic polyamide sequence is between 300 and 15000, p+q being between 1 and 100. 8. A process for the preparation of the polyesteramides and polyetheresteramides of the formula ##STR40## wherein ##STR41## represents a dicarboxylic acid polyamide sequence having a medium molecular weight between 300 and 15,000; R 3 and R 4 represent hydrogen or only one of the two represents hydrogen, the other one being an alkyl radical containing from 1 to 24 carbon atoms; R 1 is a linear or branched, saturated or unsaturated alkyl radical containing from 1 to 24 carbon atoms or an aromatic or cycloaliphatic radical; y+z has a value between 2 and 100, each being at least equal to 1; and y+z has a value between 2 and 100, each being at least n n represents the number of recurrent units that constitute the macromolecular chain; and wherein the proportion by weight of the group ##STR42## represents from 2 to 90% of the total group ##STR43## said process comprising reacting a dicarboxylic polyamide whose acid functions are situated at the ends of the chain with an α,ω diol, wherein said α,ω diol is a di beta hydroxylated tertiary amine or a polyoxyalkylene glycol containing in the chain a tertiary amine function of the formula ##STR44## wherein R 1 , R 3 , R 4 , y and z are as indicated. 9. A process according to claim 8, wherein there are reacted by weight from 98 to 10% of a dicarboxylic polyamide with from 2 to 90% of an α,ω diol. 10. A process according to claim 8, wherein the reagents are reacted substantially taking into consideration the stoichiometry between the carboxylic groups of the polyamide and the hydroxyl groups of the α,ω diol including a tertiary amine function per molecule. 11. A process according to claim 8, wherein the polycondensation is effected by mixing in a molten state the reagents in the presence of catalyst. 12. A process according to claim 8, wherein the catalyst is of the formula M(OQ) 4 wherein: M represents titanium, zirconium or hafnium and Q is a linear or branched alkyl radical having from 1 to 24 carbon atoms.
FIELD OF THE INVENTION This invention relates in general to novel polyesteramides and polyetheresteramides. In one aspect, this invention relates to a process for the preparation of polyesteramides and polyetheresteramides by the condensation of a dicarboxylic polyamide with an alpha, omega-diol. SUMMARY OF THE INVENTION The polyesteramides and polyetheresteramides of the present invention have the formula: ##STR2## wherein A designates a divalent polyamide group and ##STR3## structure derived from an α,ω diol containing in the chain a tertiary amine function to which is attached an aromatic or cycloaliphatic or alkyl radical R 1 . These polyesteramides and polyetheresteramides are obtained by the reaction of one dicarboxylic polyamide with one di beta hydroxylated tertiary amine or one polyoxyalkylene glycol including in the chain a tertiary amine function. The presence of the R 1 radical fixed on the tertiary amine function in the polymer obtained provides a polyamide possessing a good water resistance unlike the polyamides already known that are obtained by reaction of a dicarboxylic polyamide on one simple hydroxylated polyoxyalkyleneglycol, as described in French Pat. Nos. 2,401,947 and 2,273,021. DETAILED DESCRIPTION OF THE INVENTION More precisely, the products according to the invention correspond to the general formula ##STR4## wherein R 3 and R 4 represent hydrogen or only one of the two represents hydrogen, the other one being an alkyl radical containing from 1 to 24 carbon atoms, preferably containing only 1, R 1 is a linear or branched, saturated or unsaturated alkyl radical containing from 1 to 24 carbon atoms or an aromatic or cycloaliphatic radical, y+z has a value between 2 and 100, y and z individually being at least equal to 1, n represents the number of recurring units that constitute a macromolecular chain and preferably is not less than 1 with 75 as the maximum. In case y and z are equal to 1, the corresponding product is a polyesteramide. The proportion by weight of the group ##STR5## in relation to the total group ##STR6## can fluctuate from 2 to 90%, preferably from 5 to 85%. The dicarboxylic polyamide sequence ##STR7## is known per se. It usually corresponds to the group: ##STR8## wherein: R 5 is a hydrocarbon chain constituting a lactam and/or an aminoacid, the number of carbon atoms of which is preferably between 4 and 14, or the structure ##STR9## wherein R 7 and R 8 are respectively the hydrocarbon residue of a diacid and of a diamine, R 6 represents the rest of the organic diacid used as a chain limiting agent. This can be, for instance, an aliphatic, cycloaliphatic, or aromatic group, p and q, which are identical or different and one of the two can be zero, represent a repetition of a number of recurring units that constitute the macromolecular chain of the dicarboxylic polyamide sequence. The medium molecular weight of the dicarboxylic polyamide sequence is between 300 and 15,000 and preferably between 600 and 5,000, p+q are between 1 and 100 and preferably between 2 and 40. The polyesteramides and polyetheresteramides according to the invention again can generally have the formula: ##STR10## wherein R 1 , R 3 , R 4 , R 5 , R 6 , p, q, y, z and n are as defined above. The products according to the invention are obtained by reaction of a dicarboxylic polyamide whose acid functions are situated at the ends of the chain with an α,ω diol, which is either a hydroxylated di beta tertiary amine or a polyoxyalkylene glycol including in the chain a tertiary amine function. The reaction can be shown as follows: ##STR11## wherein the symbols A, R 1 , R 3 , R4, y, z and n are defined as above. When the α,ω diol is a hydroxylated di beta tertiary amine, its polycondensation with an α,ω dicarboxylic polyamide provides a polyesteramide including at least one tertiary amine function per chain. When the α,ω diol is a polyoxyalkylene glycol including in the macromolecular chain a tertiary amine function on which is fixed an alkyl, aromatic or cycloaliphatic radical, the product obtained by polycondensation with an dicarboxylic polyamide is a polyetheresteramide containing at least one tertiary amine function per chain. The test of the α,ω diol representing the group ##STR12## can be in proportion of from 2 to 90% by weight and preferably from 5 to 85% in the macro molecule of the polyamide obtained. The polycondensation reaction between the dicarboxylic polyamide and the α,ω diol, usually in respective proportions by weight comprised between 95 and 15% to 5 to 85%, is effected by mixing in a molten state the reagents in the presence of a catalyst. The condensation is usually effected while stirring at a temperture between 100° and 350° C., preferably between 180° and 300° C., within a period of from 10 minutes to 15 hours according to the nature and the weight of each one of the reagents. The reaction can be conducted at a substantially atmospheric pressure in an inert medium or under vacuum on the order of from 6 to 670 Pa. In order that the polycondensation reaction is effected under the most favorable conditions, it is recommended to react the reagents substantially taking into consideration the stoichiometry between the carboxylic groups of the polyamide and the hydroxyl groups of the α,ω diols including a tertiary amine function per molecule. The catalysts recommended for the preparation of these polyesteramides and polyetheresteramides are metal tetraalkoxides corresponding to the general formula M(OQ) 4 wherein M represents titanium, zirconium or hafnium. Within the same molecule, the identical or different Q groups designate linear or branched alkyl radicals having from 1 to 24 carbon atoms and better from 1 to 8. As examples of catalyst there can be cited Zr(OC 2 H 5 ) 4 , Zr(O-isoC 3 H 7 ) 4 , Zr(OC 4 H 9 ) 4 , Zr(OC 5 H 11 ) 4 , Zr(OC 6 H 13 ) 4 , Hf(OC 2 H 5 ) 4 , Hf(OC 4 H 9 ) 4 , Hf(O-isoC 3 H 7 ) 4 , Ti(OC 4 H 9 ) 4 . It is used alone or mixed in convenient proportion by weight of about 0.01 to 5% of the whole of the reaction medium. The dicarboxylic polyamides included in the preparation of the products of the invention are known per se. They are obtained by classical methods of preparation of such polyamides, as for example, by polycondensation of a lactam and/or an aminoacid, or of a diacid and a diamine. These polycondensations are carried out in the presence of an organic diacid whose acid functions are preferably fixed at each one of the ends of the molecule. The diacids adhere during the polycondensation as constituents of the macromolecular chain of the polyamides and they act as limiting agents of the chain, which provides the α,ω dicarboxylic polyamides. Depending on the amount of the excess of organic diacid in the polycondensation, it is possible to adjust the length of the macromolecular chain and consequently the medium molecular weight of the polyamide. The carboxylic diacids used in the synthesis reaction of the polyamide for allowing the fixation of a carboxylic group to each one of the ends of the polyamide chain, while playing the part of a limiting agent of the chain, are specially: the alkane-dioic diacids such as the succinic, adipic, suberic, azelaic, sebacic, undecanoic, dodecanoic acids or also the cycloaliphatic or aromatic diacids such as terephthalic, isophthalic, or cyclohexanedicarboxylic acids. The lactams and aminoacids used in the preparation of dicarboxylic polyamides have a hydrocarbon chain whose number of carbon atoms is preferably between 4 and 14. They are usually selected among: butyrolactam, caprolactam, oenantho lactam, decalactam, undecanolactam, dodecanolactam, 6-amino hexanoic acid, 10-amino decanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. Among the polyamides resulting from the polycondensation of a diacid with a diamine there can be cited the 6-6, 6-9, 6-10 and 6-12 nylons obtained from hexamethylene diamine and adipic, azalaic, sebacic and 1-12 dodecanoic acid or also the 9-6 nylon obtained from nonamethylene diamine and adipic acid. The dicarboxylic polyamides used in the preparation of the products of the invention have medium molecular weights that can fluctuate within a broad range. These medium molecular weights are preferably between 300 and 15,000 and preferably between 600 and 5,000. The α,ω diols used in the preparation of the products of the invention are known per se. They are obtained by adding an alkylene oxide to a primary amine according to the reaction ##STR13## wherein R 1 corresponds to a linear or branched, saturated or unsaturated, alkyl radical containing from 1 to 24 carbon atoms or an aromatic or cycloaliphatic radical, R 2 corresponds to hydrogen or to an alkyl radical containing from 1 to 24 carbon atoms knowing that R 3 =R 2 if R 4 =H and/or R 3 =H if R 4 =R 2 and x=y+z. The addition of the alkylene oxide to the primary amine results in the formation of a dihydroxylated α,ω compound in which the length of the chain that is, the medium molecular weight essentially depends on the amount of alkylene oxide added. It is also possible to cause several different alkylene oxides to react. When y and z are equal to 1 which corresponds to the addition of 2 moles alkylene oxide per mole of amine, the resulting compound is a hydroxylated di beta tertiary amine. When x is more than 2 which means that at least y or z is more than 1, the product obtained is then a polyoxyalkyleneglycol including in the macromolecular chain a tertiary amine function the position of which exclusively depends on the respective values of y and z. The primary amines capable of reacting with the alkylene oxide can be selected, for example, among the linear or branched alkane amines such as: methylamine, ethylamine, n-propylamine, n-butylamine, isobutylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, n-eicosanoylamine, n-decosanoylamine, n-tetracosanoylamine; among the amines with an unsaturated carbonated chain such as octadecyl-10-enyl-1-amine, octadecyl 10,13-dienyl-1-amine, octadecyl-10,13,16-trienyl-1-amine, among mixtures of amines with linear or branched, saturated and unsaturated, carbon chain obtained from fatty acids of copra, tallow or olein, or also among aromatic or cycloaliphatic amines such as aniline, benzylamine, orthotoluidine, and cyclohexylamine. Among the alkylene oxides that can be added to the primary amine, there are preferably chosen ethylene oxide and propylene oxide. The hydroxylated di beta tertiary amines or the polyoxyalkyleneglycols used in the preparation of the products of the invention have molecular weights that can fluctuate within a broad range. The molecular weights are preferably between 119 and 6,000 and more suitably between 119 and 3,000. The polyesteramides and polyetheresteramides of this invention are useful for a wide variety of applications. Since the compounds are thermoplastic, they can be fabricated into films, sheets, molded articles and the like, by known techniques such as extrusion or injection molding. The materials are useful as packaging materials, containers and the like. The examples that follow illustrate the invention without limiting it. In these examples: the hardness SHORE D is given according to the ASTM D 1484 standard, the stress is expressed in MPa and the elongation in percent to the threshold of flow and to the tensile strength according to the ASTM D 638 standard, the Vicat point in °C. is expressed according to the ASTM D 1525 standard, the deflection is given in mm, the stress in MPa and the module in MPa in the flexion tests according to the ASTM D 790 standard, the inherent viscosity of each polycondensate has been measured in metacresol at 20° C. (0.5 g of product per 100 g of solvent), it is expressed in dlg -1 , the melting point has been determined by differential thermal analysis. EXAMPLE 1 In a stainless steel reactor of 6 liters there are introduced 1664 g of a dicarboxylic polyamide 12 having a medium molecular weight of 2080 prepared previously by polycondensation of the dodecanolactam in the presence of adipic acid. There are then added 304 g of a mixture of oxyethylated tertiary amines having a medium molecular weight of 380 and previously obtained by adding 2.7 moles ethylene oxide to a mixture of primary amines derived from tallow fatty acids. There are also added 9.8 g tetra butylorthozirconate. After having placed the reaction medium under an inert atmosphere, it is heated until the temperature has reached 240° C. A vacuum of 27 Pa is created inside the reactor while continuing stirring strongly from the moment the constituents melt. The reaction is thus continued for 1 hour at 240° C. In proportion as the viscosity increases, the speed of stirring must be reduced. The polyesteramide is collected at the exit of the reactor in the form of liquid reeds that solidify and cool by immersion in a vat of water. The product is then granulated, dried and molded on an ARBURG press in the form of standardized test pieces that make it possible to carry out traction and flexion tests. These tests have resulted in the following values: 60 SHORE D hardness elongation in traction is 24% under 22 MPa to the flow threshold and 195% under 35 MPa to rupture, in flexion the module is 344 MPa with a stress of 10.5 MPa and a deflection of 24 mm, the Vicat point under 1 kg is 147.5° C. This polyesteramide has an inherent viscosity of 0.50 dlg -1 . Its melting point is 160° C. The polyetheresteramide corresponds to the formula: ##STR14## with p+q=9.82 and y+z=2.7 and R 1 =C 14 H 29 (2%), --C 16 H 33 (25%), --C 18 H 37 (30%), C 20 H 41 (3%) and 40% of a mixture of C 18 H 35 , --C 18 H 33 and --C 18 H 31 . EXAMPLE 2 Following a mode of operation similar to that of Example 1, 1500 g of dicarboxylic polyamide 11 resulting from the polycondensation of amino-11-undecanoic acid in the presence of adipic acid of a medium molecular weight of 2,010 are reacted with 440.3 g of a mixture of oxyethylated amines having a medium molecular weight of 590 resulting from the addition of 8.61 moles of ethylene oxide to a mixture of primary amines derived from copra fatty acids in the presence of 5.9 g of tetrabutylorthozirconate during 90 minutes at 245° C. under a pressure of 27 Pa. The polyetheresteramide prepared under these conditions has the following characteristics: ______________________________________inherent viscosity 0.80 dlg.sup.-1melting point 169° C.Vicat point under 1 kg 155° C.SHORE D hardness 54traction propertieselongation to the flow threshold 50% under 19.9 MPaelongation to rupture 40% under 39.7 MPaproperties in flexiondeflection 24 mmstress 6.6 MPamodule 242 MPa______________________________________ It corresponds to the formula ##STR15## with p+q=10.19; y+z=8.61 and R 1 =--C 10 H 21 (3%), --C 12 H 25 (60%), --C 14 H 29 (20%), --C 16 H 33 (10%) and --C 18 H 37 (7%). EXAMPLE 3 Following the mode of operation of Example 1, 1620 g of a dicarboxylic polyamide 6 obtained by polycondensation of the caprolactam in the presence of adipic acid, having a medium molecular weight in 1540, are reacted with 399.75 g of the mixture of oxyethylated tertiary amines used in Example 1 in the presence of 21 g of tetrabutylorthozirconate. The duration of reaction at 250° C. and under extensive vacuum is of 8 hours. The melting point of the polymer obtained is 200° C. and it has the following characteristics: ______________________________________SHORE D hardness 62inherent viscosity 0.70 dlg.sup.-1Vicat point under 1 kg 174° C.properties in tractionelongation to the flow threshold 18% under 21.4 MPaelongation to rupture 340% under 30 MPaproperties in flexiondeflection 25 mmstress 9.4 MPamodle 327 MPa______________________________________ The polyetheresteramide corresponds to the formula: ##STR16## with p+q=12.34 and y+z=2.7 and R 1 =--C 14 H 29 (2%), --C 16 H 33 (25%), --C 18 H 37 (30%), C 20 H 41 (3%) and 40% of a mixture of C 18 H 35 , --C 18 H 33 and --C 18 H 31 . EXAMPLE 4 In a stainless steel reactor of 6 liters there are introduced 1900 g of the dicarboxylic polyamide 12 used in Example 1. There are added 108.7 g N-methyl diethanolamine and 15.46 g tetrabutylorthozirconate. After having placed the reaction medium under inert atmosphere, it is heated until the temperature has reached 210° C. After 1 hour at this temperature, a vacuum is created inside the reactor proceeding by stages while increasing the temperature of the reaction medium to 240° C. The reaction is thus continued for 3 hours under a pressure of 40 Pa. The polyesteramide prepared under these conditions has the following characteristics: ______________________________________SHORE D hardness 66inherent viscosity 0.50 dlg.sup.-1Vicat point under 1 kg 154° C.melting temperature 163° C.properties in tractionelongation to the flow threshold 12.5% under 26 MPaelogation to rupture 371% under 36.5 MPaproperties in flexiondeflection 27 mmstress 15 MPamodule 490 MPa______________________________________ The polyetheresteramide corresponds to the following formula: ##STR17## with p+q=9.82 and y=Z=1. EXAMPLES 5 TO 11 Following the mode of operation of Example 1, a dicarboxylic polyamide 6, 11 or 12 previously obtained by polycondensation of the caprolactam, amino-11undecanoic acid or dodecanolactam, respectively, in the presence of adipic acid is reacted with a mixture of oxyethylated amines obtained by addition of n moles of ethylene oxide to a mixture of primary amines derived from fatty acids of tallow, olein or copra in the presence of tetrabutylorthozirconate. In Table 1 are stated for each example, the nature of the polyamide and of the mixture of oxyethylated amines, the respective medium molecular eight thereof, the quantity of each one of these products, including the catalyst, introduced in the reactor, the duration and temperature of reaction. For each reaction the vacuum has been made inside of the reactor starting when the desired temperature is reached. The duration of the reaction corresponds to the period of time between the start of the vacuum and the recovery of the polymer in the form of liquid reeds that solidify and cool by immersion in a vat of water. The characteristics of each product analyzed are set forth in Table 2. The products obtained correspond to the following formulae: Formula of the polyetheresteramide obtained in Example No. 5 ##STR18## with p+q=9.41 and y+z=5 and R 1 =--C 14 H 29 (2%), --C 16 H 33 (25%), --C 18 H 37 (30%) --C 20 H 41 (3%) and 40% of a mixture of --C 18 H 35 , --C 18 H 33 and --C 18 H 31 . Formula of the polyetheresteramide obtained in Example No. 6 ##STR19## with p+q=10.13 and y+z=5 and R 1 =--C 10 H 21 (3%), --C 12 H 25 (60%), --C 14 H 29 (20%) --C 16 H 33 (10%), and --C 18 H 37 (7%). Formula of the polyetheresteramide obtained in Example No. 7 ##STR20## with p+q=10.13 and y+z=4.27 and R 1 =--C 16 H 33 (15%), --C 18 H 37 (5%) and 80% of a mixture of --C 18 H 35 , --C 18 H 33 and --C 18 H 31 . Formula of the polyetheresteramide obtained in Example No. 8 ##STR21## with p+q=10.13 and y+z=11 and R 1 =--C 14 H 29 (2%), --C 16 H 33 (25%), --C 18 H 37 (30%) --C 20 H 41 (3%) and 40% of a mixture of --C 18 H 35 , --C 18 H 33 and --C 18 H 31 . Formula of the polyetheresteramide obtained in Example No. 9 ##STR22## with p+q=3.83 and y=z=1 and R 1 =--C 10 H 21 (3%), --C 12 H 25 (60%), --C 14 H 29 (20%) --C 16 H 33 (10%), and --C 18 H 37 (7%). Formula of the polyetheresteramide obtained in Example No. 10 ##STR23## with p+q=9.675 and y+z=7.25 and R 1 =--C 14 H 29 (2%), --C 16 H 33 (25%), --C 18 H 37 (30%) --C 20 H 41 (3%) and 40% of a mixture of --C 18 H 35 , --C 18 H 33 and --C 18 H 31 . Formula of the polyetheresteramide obtained in Example 11 ##STR24## with p+q=9.675 and y+z=9.52 and R 1 =--C 14 H 29 (2%), --C 16 H 33 (25%), --C 18 H 37 (30%) --C 20 H 41 (3%) and 40% of a mixture of --C 18 H 35 , --C 18 H 33 and --C 18 H 31 . TABLE 1__________________________________________________________________________Dicarboxylic Mixture ofPolyamide oxyethylated amines Quantity introduced Medium Nature Medium in the reactor Temperature molecular of the molecular g of Duration ofExample weight fatty weight Polyamide Oxyethylated reaction reactionno Nature g acids n g diacid Amines Zr(OBu).sub.4 (°C.) (min.)__________________________________________________________________________5 6 2 340 TALLOW 5 480 1 638 336 20 245 2606 11 2 000 COPRA 5 420 1 640 344.4 10.3 250 1607 11 2 000 OLEIC 4.27 450 1 600 360 17.6 245 4008 11 2 000 TALLOW 11 745 1 500 558.75 10.3 240 2359 12 900 COPRA 2 290 1 548 498.8 23.3 240 36510 12 2 050 TALLOW 7.25 580 1 681 475.6 12.3 235 25511 12 2 050 TALLOW 9.52 680 1 476 489.6 6.5 235 55__________________________________________________________________________ TABLE 2__________________________________________________________________________ Properties of tractionMelting Vicat To flow threshold To rupture Properties of flexionTempera- Inherent point Elonga- Elonga- Deflec-Exampleture Viscosity SHORE D under 1 Kg tion Stress tion Stress tion Stress Moduleno. °C. dlg.sup.-1 Hardness °C. % MPa % MPa mm MPa MPa__________________________________________________________________________5 202 0.77 63 180 40 22.2 235 35.6 23.4 11.7 4166 170 0.51 59 152 70 21.2 364 32.6 25.5 8.9 3247 170 0.50 58 155 40 21.8 235 22.4 28.9 8.6 2648 170 0.68 55 155 26 16.0 404 36.0 24.0 6.0 2099 145 0.48 51 110 18 12.0 360 23.0 27.0 6.0 19410 158 0.51 58 147 18 18.0 305 28.0 26.0 10.0 29311 158 0.85 55 144 40 17.8 453 34.8 27.5 7.9 256__________________________________________________________________________ Resistance to water during 7 days at 25° C. of the polyesteramides and polyetheresteramides obtained In order to assess this property, 5 standardized test samples of the different polyesteramides and polyetheresteramides prepared according to the procedures described in Examples 1 to 11 were immersed in water for 7 days at 25° C. By way of comparison, the same test was effected with polyetheresteramides (PEEA 1 to 6) prepared according to the procedures described in French Pat. No. 2,273,021. The products obtained were granulated, dried and ground on an ARBURG press in the form of standardized test samples. The measures of control and identification of the products obtained are: inherent viscosity measured in the meta-cresol at 20° C. (0.5 g of product per 100 g of solvent). It is expressed in dlg -1 . the melting temperature of the polycondensate, determined by differential thermal analysis. the SHORE D hardness according to the ASTM D 1484 standard. PEEA 1 results from the polycondensation of 1400 g of a dicarboxylic polyamide 12 of a molecular weight of 2000 obtained from dodecalactam and adipic acid with 280 g of a polyoxyethyleneglycol of a medium molecular weight of 400. The polyetheresteramide obtained has an inherent viscosity of 1.33 dlg -1 , a melting temperature of 158° C. and a SHORE D hardness of 59. It corresponds to the following formula: ##STR25## with p+q=9.41 and r=8.68. PEEA 2 results from the polycondensation of 1400 g of the dicarboxylic polyamide 12 used in the preparation of PEEA 1 with 420 g of a polyoxyethylene glycol having a medium molecular weight of 600. The polyether-ester-amide obtained has an inherent viscosity of 1.14 dlg -1 , a melting temperature of 168° C. and a SHORE D hardness of 58. It corresponds to the following formula: ##STR26## with p+q=9.41 and r=13.23. PEEA 3 results from the polycondensation of 1000 g of a dicarboxylic acid polyamide 12 having a medium molecular weight of 850 obtained from dodecanolactam and adipic acid with 470.6 g of the polyoxyethylene glycol used in the preparation of PEEA 1. The resulting polyetheresteramide has an inherent viscosity of 0.81 dlg -1 , a melting temperature of 138° C. and a SHORE D hardness of 44. It corresponds to the following formula: ##STR27## with p+q=3.57 and r=8.68. PEEA 4 results from the polycondensation of 918 g of the dicarboxylic polyamide 12 used in the preparation of PEEA 3 with 648 g of the polyoxyethylene glycol used in the preparation of PEEA 2. The polyetheresteramide obtained has an inherent viscosity of 0.96 dlg -1 , a melting temperature of 145° C. and a SHORE D hardness of 42. It corresponds to the following formula: ##STR28## with p+q=3.57 and r=13.23. PEEA 5 results from the polycondensation of 1300 g of a dicarboxylic polyamide 11 having a medium molecular weight of 2000, prepared from amino-11-undecanoic acid and adipic acid and 260 g of the polyoxyethylene glycol used in the preparation of PEEA 3. The polyetheresteramide obtained has an inherent viscosity of 0.87 dlg -1 , a melting temperature of 175° C. and a SHORE D hardness of 56. It corresponds to the following formula: ##STR29## with p+q=10.13 and r=8.68. PEEA 6 results from the polycondensation of 1309 g of a dicarboxylic polyamide 6 having a medium molecular weight of 1540, prepared from caprolactam and adipic acid with 340 g of the polyoxyethylene glycol used in the preparation of PEEA 5. The polyetheresteramide obtained has an inherent viscosity of 1.03 dlg -1 , a melting temperature of 202° C. and a SHORE D hardness of 56. It corresponds to the following formula: ##STR30## with p+q=12.34 and r=8.68. The recovery in weight after 7 days at 25° C., in water, of the polyesteramides and polyetheresteramides of Examples 1 to 11 and of the polyetheresteramides PEEA 1 to 6 is given in the following table: TABLE 3______________________________________Polyesteramides andPolyetheresteramides Polyetheresteramides ##STR31## ##STR32## Recovery in Recovery inExample no. weight % n° of PEEA weight %______________________________________1 0.57 1 3.972 3.003 3.59 2 10.014 0.765 17.60 3 10.766 0.827 0.85 4 27.458 2.929 0.74 5 4.7110 1.2411 4.00 6 21.31______________________________________

Description

Topics

Download Full PDF Version (Non-Commercial Use)

Patent Citations (2)

    Publication numberPublication dateAssigneeTitle
    US-2812313-ANovember 05, 1957Bayer AgCopolymers of amino-group-containing polyesters
    US-3555114-AJanuary 12, 1971Allied ChemPolycaprolactam polymerized with diethanolamine

NO-Patent Citations (0)

    Title

Cited By (87)

    Publication numberPublication dateAssigneeTitle
    US-6239216-B1May 29, 2001AtofinaThermoplastics with improved flexibility and transparency
    US-2010125002-A1May 20, 2010Taylor Made Golf Company, Inc.Resin compositions incorporating modified polyisocyanate and method for their manufacture and use
    US-2006020060-A1January 26, 2006General Electric CompanyAnti-static flame retardant resin composition and methods for manufacture thereof
    US-7014919-B2March 21, 2006RkemaPolyamide-based transparent composition
    US-5130382-AJuly 14, 1992Texaco Chemical CompanyHydroxy terminated polyoxypropylene polyamides
    US-8575278-B2November 05, 2013Taylor Made Golf Company, Inc.Ionomer compositions for golf balls
    US-5998545-ADecember 07, 1999Elf Atochem S.A.Mixtures of polymer having polyamide blocks and copolymers having vinylaromatic units and anhydride units
    US-5986005-ANovember 16, 1999Elf Atochem S.A.Composition including a fluoroelastomer and a thermoplastic polyamide and resulting film
    US-7169453-B2January 30, 2007Arkema FranceMultilayer structure and tank consisting of this structure, which has a barrier layer in direct contact with the fluid contained
    US-9174099-B2November 03, 2015Taylor Made Golf Company, Inc.Golf club face
    US-2004262581-A1December 30, 2004Rodrigues David E.Electrically conductive compositions and method of manufacture thereof
    US-9682291-B2June 20, 2017Taylor Made Golf Company, Inc.Golf club face with cover having roughness pattern
    US-5543489-AAugust 06, 1996Alex; Patrick, Aubert; Yves, Frey; AlainNon-exuding thermoplastic elastomers
    US-2009163289-A1June 25, 2009Taylor Made Golf Company, Inc.Method of creating scorelines in club face insert
    US-7879968-B2February 01, 2011Taylor Made Golf Company, Inc.Polymer compositions and golf balls with reduced yellowing
    WO-2006024715-A1March 09, 2006ArkemaFluid transporting tube
    WO-2011124833-A1October 13, 2011Arkema FranceBlock copolymer derived from renewable materials and method for making such a block copolymer
    US-6127456-AOctober 03, 2000Elf Atochem SaMultiphase thermoplastic resin compositions
    WO-2016099878-A1June 23, 2016Zephyros, Inc.Epoxy composition containing copolyamide and block copolymer with polyamide and polyether blocks
    US-8113966-B2February 14, 2012Taylor Made Golf Company, Inc.Golf ball having cross-core hardness differential and method for making it
    US-7582342-B2September 01, 2009Degussa AgMolding composition based on polyetheramides
    WO-2014057462-A1April 17, 2014Sabic Innovative Plastics Ip B.V.Antistatic flame retardant resin composition and methods and uses thereof
    WO-2012120114-A1September 13, 2012L'orealProcédé de traitement cosmétique de la transpiration humaine qui comprend l'application d'un film polymère antiperspirant solubilisable
    US-5504142-AApril 02, 1996Elf Atochem S.A.Device for controlling insects
    US-7026432-B2April 11, 2006General Electric CompanyElectrically conductive compositions and method of manufacture thereof
    EP-3196226-A1July 26, 2017Arkema FranceBlock copolymer obtained from renewable materials and method for manufacturing such a block copolymer
    US-6759480-B1July 06, 2004AtofinaThermoplastic resins modified by copolymers based on heavy acrylates
    US-8481621-B2July 09, 2013Taylor Made Golf Company, Inc.Compositions comprising an amino triazine and ionomer or ionomer precursor
    US-2004011999-A1January 22, 2004Murray Michael C.Antistatic flame retardant resin composition and methods for manufacture thereof
    WO-2010086574-A2August 05, 2010Arkema FranceProcede de synthese d'un alliage de copolymere a blocs presentant des proprietes antistatiques ameliorees
    US-8674023-B2March 18, 2014Taylor Made Golf Company, Inc.Ionomer compositions for golf balls
    US-2005070657-A1March 31, 2005Mark Elkovitch, Soumyadeb Ghosh, Nitin Mutha, Srinivasan Rajagopalan, Sai-Pei TingConductive thermoplastic compositions, methods of manufacture and articles derived from such compositions
    US-2004232389-A1November 25, 2004Elkovitch Mark D.Electrically conductive compositions and method of manufacture thereof
    US-2006069199-A1March 30, 2006Charati Sanjay G, Dibakar Dhara, Soumyadeb Ghosh, Nitin Mutha, Srinivasan Rajagopalan, Shaikh Abbas A, Elkovitch Mark DElectrically conductive compositions and method of manufacture thereof
    EP-0780594-A1June 25, 1997Elf Atochem S.A.Courroies antistatiques
    US-9260602-B2February 16, 2016Sabic Global Technologies B.V.Antistatic flame retardant resin compositions and methods and uses thereof
    US-6203920-B1March 20, 2001Elf Atochem S.A.Flexible, polyamide-based compositions suitable for extrusion blow moulding
    US-7309727-B2December 18, 2007General Electric CompanyConductive thermoplastic compositions, methods of manufacture and articles derived from such compositions
    EP-1783156-A1May 09, 2007Arkema FranceVerfahren zur Herstellung von Copolymeren mit Polyamid-und Polyetherblöcken
    US-9339696-B2May 17, 2016Acushnet CompanyThree-cover-layer golf ball comprising intermediate layer including a plasticized polyester composition
    US-7354988-B2April 08, 2008General Electric CompanyElectrically conductive compositions and method of manufacture thereof
    US-5506024-AApril 09, 1996AtochemPolyetheresteramide-based water vapor permeable thermoplastic elastomer film, process for its manufacture and articles comprising said film
    EP-2090629-A2August 19, 2009Arkema FranceUtilisation d'un promoteur d'adhérence dans une solution de nettoyage
    US-8629228-B2January 14, 2014Taylor Made Golf Company, Inc.Ionomer compositions for golf balls
    US-8628434-B2January 14, 2014Taylor Made Golf Company, Inc.Golf club face with cover having roughness pattern
    US-6121374-ASeptember 19, 2000Elf Atochem SaFlexible thermoplastic resins with improved tensile strength
    US-2005038225-A1February 17, 2005Charati Sanjay Gurbasappa, Dibakar Dhara, Mark Elkovitch, Soumyadeb Ghosh, Nitin Mutha, Srinivasan Rajagopalan, Shaikh Abbas AlliElectrically conductive compositions and method of manufacture thereof
    US-6045919-AApril 04, 2000Elf Atochem S.A.Antistatic film for packaging materials diffusing volatile products
    US-8030411-B2October 04, 2011Taylor Made Golf Company, Inc.Polymer compositions comprising peptizers, sports equipment comprising such compositions, and method for their manufacture
    US-7462656-B2December 09, 2008Sabic Innovative Plastics Ip B.V.Electrically conductive compositions and method of manufacture thereof
    US-2009163291-A1June 25, 2009Taylor Made Golf Company, Inc.Golf club face with cover having roughness pattern
    EP-0693367-A1January 24, 1996Elf Atochem S.A.Polymer auf der Basis von Polyamid enthaltendem Material, welches auf EPDM-Kautschuk haftet
    US-2005014842-A1January 20, 2005Degussa AgMolding composition based on polyetheramides
    US-2003100656-A1May 29, 2003Eastman Kodak CompanySmectite clay intercalated with polyether block polyamide copolymer
    US-2003181568-A1September 25, 2003Jayantha Amarasekera, Kim Balfour, Christian LietzauConductive plastic compositions and method of manufacture thereof
    US-2002051891-A1May 02, 2002Elf Atochem S.A.Multilayer structure and tank consisting of this structure, which has a barrier layer in direct contact with the fluid contained
    US-2004211942-A1October 28, 2004Clark Darren Cameron, Mark Elkovitch, Soumyadeb Ghosh, Srinivasan Rajagopalan, Sai-Pei TingElectrically conductive compositions and method of manufacture thereof
    US-9669265-B2June 06, 2017Acushnet CompanyThree-cover-layer golf ball having transparent or plasticized polyamide intermediate layer
    US-2009134370-A1May 28, 2009Herve Cartier, Alexis ChopinConductive halogen free flame retardant thermoplastic composition
    WO-2015067880-A1May 14, 2015Arkema FranceImpact-resistant thermoplastic composition
    US-8764586-B2July 01, 2014Taylor Made Golf Company, Inc.Golf ball having cross-core hardness differential and method for making it
    EP-1243831-A1September 25, 2002AtofinaTube multicouche en matière plastique pour le transfert de fluides
    EP-1243832-A1September 25, 2002AtofinaTube multicouche à base de polyamides et de fluoropolymère pour le transport d'essence
    EP-0656388-A1June 07, 1995Elf Atochem S.A.Alliages de thermoplastique et caoutchouc adhérents sur des thermoplastiques
    US-8211976-B2July 03, 2012Taylor Made Golf Company, Inc.Sports equipment compositions comprising a polyurethane, polyurea or prepolymer thereof and a polyfunctional modifier
    EP-0437981-A1July 24, 1991Texaco Chemical CompanyPolyamide esters, leurs procédés de manufacture et intermédiaires pour ces procédés
    US-7166656-B2January 23, 2007Eastman Kodak CompanySmectite clay intercalated with polyether block polyamide copolymer
    WO-2006046571-A1May 04, 2006Unitika Ltd., Arkema Kabushiki Kaishaポリアミド樹脂組成物から成る靴底と、それを用いた靴
    US-7018567-B2March 28, 2006General Electric CompanyAntistatic flame retardant resin composition and methods for manufacture thereof
    US-6025055-AFebruary 15, 2000Elf Atochem,S.A.Flexible, polyamide-based compositions suitable for extrusion blow moulding
    US-8096899-B2January 17, 2012Taylor Made Golf Company, Inc.Golf ball comprising isocyanate-modified composition
    US-6528615-B2March 04, 2003AtofinaCopolymers containing polyamide blocks and polyether blocks based on ethoxylated amines
    US-8927651-B2January 06, 2015Rhodia OperationsHigh-viscosity polyamide composition
    WO-2011073356-A2June 23, 2011L'orealUse of a cosmetic composition comprising at least one film-forming elastomeric polymer for treating human perspiration.
    EP-0688826-A1December 27, 1995Elf Atochem S.A.Film imper-respirant
    US-2007142568-A1June 21, 2007Taylor Made Golf Company, Inc.Polymer compositions comprising peptizers, sports equipment comprising such compositions, and method for their manufacture
    EP-3085725-A1October 26, 2016Arkema FranceCopolymer in blockform, das aus erneuerbaren materialien hervorgeht, und herstellungsverfahren eines solchen copolymers in blockform
    US-2006183817-A1August 17, 2006Keulen Jan P, Koevoets Christiaan H JElectrically conductive compositions and method of manufacture thereof
    EP-2502950-A1September 26, 2012Arkema FranceProcédé de synthèse d'un alliage de copolymère à blocs présentant des propriétés antistatiques améliorées
    US-2005029498-A1February 10, 2005Mark Elkovitch, Srinivasan Rajagopalan, Soumyadeb Ghosh, Mutha Nitin HiralalElectrically conductive compositions and method of manufacture thereof
    WO-2011151203-A2December 08, 2011L'orealProcessus de traitement cosmétique utilisant un revêtement à base d'un copolymère contenant des blocs de polyamide et des blocs de polyéther
    US-8912286-B2December 16, 2014Taylor Made Golf Company, Inc.Polymer compositions comprising peptizers, sports equipment comprising such compositions, and method for their manufacture
    EP-1452333-A2September 01, 2004Eastman Kodak CompanyVerfahren zur Herstellung eines Bildaufzeichnungselements, das eine extrudiertes Polyester enthaltende Bildempfangsschicht umfasst
    EP-0787761-A1August 06, 1997Elf Atochem S.A.Films based on polyamides and polyolefins
    US-2013131269-A1May 23, 2013Rhodia OperationsHigh-viscosity polyamide composition
    EP-0705883-A1April 10, 1996Elf Atochem S.A.Carte antistatique
    US-6528572-B1March 04, 2003General Electric CompanyConductive polymer compositions and methods of manufacture thereof