Impact-modified polyamide compositions

Abstract

Described herein are polyamide compositions and processes for producing polyamide compositions, comprising: (i) a polyamide, (ii) an olefin-maleic anhydride copolymer (on its own or in a master batch form), and (iii) an impact modifier (or an elastomeric polymer with an optional compatibilizer), which exhibit enhanced ambient and low temperature impact strength complimented by excellent thermal, tensile and flexural properties.

Claims

1. A polyamide composition produced by a process comprising the step of compounding a mixture comprising a polyamide, a 1:1 alternating olefin-maleic anhydride copolymer, wherein the olefin is selected from the group consisting of ethylene, propylene, isobutylene, 1-butene, 1-octene, butadiene, isoprene, 1-hexene, 1-dodecene, dodecene-1, and 1-tetradecene, and an impact modifier selected from the group consisting of a grafted-maleic anhydride elastomer and a grafted-maleic anhydride terpolymer.

2. The polyamide composition of claim 1, wherein the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6and nylon 6-6, nylon-9, nylon-10, nylon-11, nylon-12, nylon 6-10, aromatic polyamides, elastomeric polyamides, and mixtures thereof.

3. The polyamide composition of claim 1, wherein the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6and nylon 6 6, and mixtures thereof.

4. The polyamide composition of claim 1, wherein the polyamide is recycled polyamide.

5. The polyamide composition of claim 1, wherein the olefin is ethylene.

6. The polyamide composition of claim 1, wherein the olefin-maleic anhydride copolymer has a weight average molecular weight of about 1000 to about 900,000.

7. The polyamide composition of claim 1, wherein the olefin-maleic anhydride copolymer has a weight average molecular weight of about 60,000 to about 400,000.

8. The polyamide composition of claim 1, further comprising one or more stabilizing agents.

9. The polyamide composition of claim 8, wherein each of the one or more stabilizing agents is independently selected from the group consisting of cuprous iodide, potassium iodide, tris-(2,4-di-tert-butylphenyl)phosphite, and N,N-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)).

10. The polyamide composition of claim 8, wherein each of the one or more stabilizing agents independently has a concentration of about 0.01 to about 1.0% w/w of the polyamide composition.

11. The polyamide composition of claim 1, further comprising a compatibilizer selected from the group consisting of acrylic acid modified polypropylene homopolymer, maleic anhydride modified polypropylene homopolymer, ethylene acrylic acid copolymer, and ethylene-octene copolymer grafted with maleic anhydride.

12. The polyamide composition of claim 1, wherein the impact modifier is a grafted-maleic anhydride elastomer or a grafted-maleic anhydride terpolymer having a maleic anhydride content of from about 0.5% to about 5%.

13. The polyamide composition of claim 12, wherein the impact modifier is a grafted-maleic anhydride elastomer or terpolymer having a maleic anhydride content in the range of 0.8 to 2%.

14. The polyamide composition of claim 1, further comprising one or more additives selected from the group consisting of a UV stabilizer, a halogenated or non-halogenated flame retardant additive, a reinforcement material, a heat stabilizer, a light stabilizer, a polymerization regulator, a plasticizer, a lubricant, a rheology modifier, a friction modifier, an anti-blocking agent, an antioxidant, an antistatic agent, a UV absorber, a pigment, and a dye.

15. The polyamide composition of claim 14, wherein the reinforcement is a mineral, a glass fiber, a glass fabric, a glass roving filament, a glass tube, a glass yarn, carbon, graphite, or cellulose.

16. The polyamide composition of claim 1, wherein the impact modifier is selected from the group consisting of a rubber copolymer produced in a reactor from ethylene and propylene (EPR) grafted with maleic anhydride, a rubber terpolymer of ethylene, propylene and diene-modifier (EPDM) grafted with maleic anhydride, and an ethylene alpha-olefin copolymer grafted with maleic anhydride.

17. An article comprising a polyamide composition according to claim 1.

18. A polyamide composition produced by a process comprising the steps of: (a) preparing a master batch composition comprising an impact modifier selected from the group consisting of a grafted-maleic anhydride elastomer and a grafted-maleic anhydride terpolymer and a 1:1 alternating olefin-maleic anhydride copolymer, wherein the olefin is selected from the group consisting of ethylene, propylene, isobutylene, 1-butene, 1-octene, butadiene, isoprene, 1-hexene, 1-dodecene, dodecene-1, and 1-tetradecene; and (b) compounding a polyamide with the master batch composition.

19. The polyamide composition of claim 18, wherein the impact modifier is a grafted-maleic anhydride elastomer or a grafted-maleic anhydride terpolymer having a maleic anhydride content of from about 0.5% to about 5%.

20. The polyamide composition of claim 18, wherein the impact modifier is a grafted-maleic anhydride elastomer or terpolymer having a maleic anhydride content in the range of 0.8 to 2%.

21. The polyamide composition of claim 18, wherein the impact modifier is selected from the group consisting of a rubber copolymer produced in a reactor from ethylene and propylene (EPR) grafted with maleic anhydride, a rubber terpolymer of ethylene, propylene and diene-modifier (EPDM) grafted with maleic anhydride, and an ethylene-alpha-olefin copolymer grafted with maleic anhydride.

22. The polyamide composition of claim 18, wherein the master batch further comprises one or more stabilizing agents.

23. The polyamide composition of claim 22, wherein the one or more stabilizing agents is selected from the group consisting of cuprous iodide, potassium iodide, tris-(2,4-di-tert-butylphenyl)phosphite, and N,N-hexane- 1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)).

24. The polyamide composition of claim 18, wherein the master batch further comprises one or more compatibilizers selected from the group consisting of acrylic acid modified polypropylene homopolymer, maleic anhydride modified polypropylene homopolymer, ethylene acrylic acid copolymer, and ethylene-octene copolymer grafted with maleic anhydride.

25. The polyamide composition of claim 18, wherein the master batch further comprises one or more stabilizing agents and one or more compatibilizers selected from the group consisting of acrylic acid modified polypropylene homopolymer, maleic anhydride modified polypropylene homopolymer, ethylene acrylic acid copolymer, and ethylene-octene copolymer grafted with maleic anhydride.

Description

METHODS AND EXAMPLES

(1) Materials

(2) Polyamide 6 (grade PA6 NG320HSL) which is recycled quality was obtained from Jamplast Inc. and was used as received. The other Polyamide-6 used were prime (also called virgin Nylon-6) grade from BASF called Ultramid? B3S and Ultramid? B24 NO2. Polyamide-6,6 used was a prime (also called virgin Nylon-66) grade from BASF called Ultramid? A3K. Care was taken to ensure that all grades stayed dry.

(3) A 1:1 ethylene-maleic anhydride alternating copolymer grade ZeMac? E-60 (E-60) from Vertellus Specialties Inc. with a weight average molecular weight (MWw) of 60,000 was used in illustrative examples. A 1:1 ethylene-maleic anhydride alternating copolymer grade ZeMac? E-400 (E-400) from Vertellus Specialties Inc. with a weight average molecular weight (MWw) of 400,000 was also used in other illustrative examples.

(4) Fusabond? N493 (Ethylene-Octene-g-MAh) from DuPont, Royaltuf? 485 (EPDM-g-MAh) from Addivant and Amplify GR216 (a plastomer grafted with maleic anhydride) from The Dow Chemical Co. were used as commercially available impact modifiers.

(5) Royalene? IM7200 pellets from Lion Copolymer, Optema? grade TC 141, an ethylene-methyl acrylate copolymer resin from ExxonMobil Chemicals with a melt index of 110 g/min and Lotryl? grade 28BA175 an ethylene-butyl acrylate copolymer were used as representatives of the elastomers without maleic anhydride grafting.

(6) Amplify? GR205 (high density polyethylene grafted with maleic anhydride) from The Dow Chemical Co. was used as a representative non-elastomeric graft copolymer, used as a compatibilizer.

(7) Optema? grade TC 141, ethylene-methyl acrylate copolymer resin from ExxonMobil Chemicals with a melt index of 110 g/min and Amplify? GR216 (a plastomer grafted with maleic anhydride) from The Dow Chemical Co. were used as carrier resins for the master batch formulations.

(8) Glass Fiber grade used was ECS 03 T275H from NEG and fed downstream into the melt with a side feeder during compounding.

(9) Testing

(10) The following TABLE 1 shows the test methods used and the corresponding ASTM methods.

(11) TABLE-US-00001 TABLE 1 Tests ASTM Method & Conditions Tensile Strength, & Elongation D 638 at room temperature (23? C.) Flexural Modulus & Strength D 790 at room temperature (23? C.) Notched Izod Impact Strength D 256 at room temperature (23? C. & ?30? C.) Notched Charpy Impact Strength ISO 179-2/2 at room temperature (23? C. & ?30? C.) Heat Deflection Temperature ASTM D648 at room temperature (HDT) (23? C.)
Compounding with Elastomeric Polymer, Olefin-Maleic Anhydride and Polyamide

(12) Compounding was carried out using a counter-rotating inter-meshing twin screw extruder (Berstorff 25 mm.) with the temperature profile of 220, 235, 255, 245, 240, 240, 240, and 260? C. cooled in a water bath and pelletized. A two-feeder system was used to feed the hopper for the compounding. The additives (e.g. stabilizer such as anti-oxidant and heat stabilizers) were pre-mixed with olefin-maleic anhydride copolymers and fed through one feeder while carrier resin and other pellets described herein was fed through the other. The resulting pellets were dried for 12 hours at 70? C. to remove retained moisture. The formulations are shown in the TABLE 2. The virgin nylon-6 used was Ultramid? B3S and the EPDM pellets used were Royalene? IM 7200 both described herein. The high density polyethylene grafted maleic anhydride used showing the optional use of a compatibilizer was Amplify? GR 205 (POE-g-MAh). The stabilizers used and the ethylene-maleic anhydride alternating copolymers used are also described herein.

(13) TABLE-US-00002 TABLE 2 Stabilizer Package Hindered Virgin EPDM POE-g- Phosphite Phenol Example # Nylon-6 Pellets E-60 E-400 MAh CuI KI Stabilizer AO 1 (control) 74% 25% 0.01% 0.09% 0.4% 0.5% 2 72% 25% 2.0% 0.01% 0.09% 0.4% 0.5% 3 72% 25% 2.0% 0.01% 0.09% 0.4% 0.5% 4 72% 25% 2.0% 0.01% 0.09% 0.4% 0.5%

(14) TABLE-US-00003 TABLE 3 ASTM D256 Izod Izod ISO 179-2/2 ASTM D638 ASTM D 790 Impact Impact Charpy Charpy Tensile Flexural Strength Strength Impact Impact Strenth Tensile Tensile Flexural Strength @ @ 23? C. @ ?30? C. Strength Strength @ Yield Elongation Modulus Modulus Break (ft- (ft- @ 23? C. @?30? C. Example # (MPa) (%) (MPa) (MPa) (MPa) lb/in) lb/in) (KJ/m.sup.2) (KJ/m.sup.2) 1 37.77 8.57 1492.6 1402.8 29.96 0.82 0.55 6.47 6.31 (control) (CB) (CB) (CB) (CB) 2 45.96 7.27 1703 1913.3 63.77 1.21 0.74 7.16 5.60 (CB) (HB) (CB) (CB) 3 46.58 10.18 1701.8 1871.5 62.74 1.24 0.73 9.54 9.53 (CB) (HB) (CB) (CB) 4 37.6 29.25 1404.2 1498.8 50.08 2.93 1.80 30.70 31.1 (CB) (CB) (NB) (NB) CB indicates complete break, HB indicates some of the specimen broke while the others did not and NB indicates no break for the impact strength values.

(15) After compounding and testing, the results obtained are shown in TABLE 3. The data for Example 2, 3 and 4 show improvements in most properties compared to Example 1 (control). Overall impact strength is improved; the improvement is higher for the composition with the compatibilizer, Example 4, and less for the non-compatibilized compositions in Example 2 and 3. Tensile strength for the composition in Example 3 is higher and much more so for that in Example 4. Similarly the flexural strength at break is also higher for the compositions in Examples 2 and 3. The unexpected result is that other properties such as tensile strength and flexural modulus which typically decrease actually improve in spite of the 25% of elastomeric component in the compositions of this invention. The processes and compositions described herein can be extended to using other elastomeric systems such as plastomers and combination of elastomers to boost the mechanical properties in presence of ethylene-maleic anhydride alternating copolymer of the current invention.

(16) Additional compounding examples described in TABLES 4 and 6 were carried out using a counter-rotating inter-meshing twin screw extruder (Coperion ZSK-40) with virgin Polyamide-6 using the temperature settings of 230, 240, 240, 240, 240, 250, 250, 250, 250, 250, 245, 240? C. and virgin Polyamide-6,6 with NEG's glass fiber fed through side feeder (Grade ECS 03 T275H) using temperature settings of 243, 254, 262, 268, 274, 281, 280, 276, 271, 274? C. In both these experiments commercially available grafted maleic anhydride copolymers Fusabond? N493 (PE-g-MAh) and Royaltuf? 485 (EPDM-g-MAh) were used.

(17) TABLE-US-00004 TABLE 4 Virgin Example # Nylon-6 E-60 PE-g-MAh EPDM-g-MAh 9 (control) 85.0% 15% 10 84.36% 0.64% 15% 11 (control) 85.0% 15% 12 84.36% 0.64% 15%

(18) TABLE 5 shows test results for the materials obtained after compounding and injection molding the compositions shown in TABLE 4. Example 9 and 11 are controls whose mechanical properties at both room temperature and low temperature at ?30? C. are compared to the properties obtained from Examples 10 and 12 containing E-60. Both Examples 10 and 12 show marked improvement in room temperature impact resistance, in addition to improvements in low temperature impact resistance, tensile strength, elongation and flexural modulus.

(19) TABLE-US-00005 TABLE 5 ASTM D638 ASTM D256 Tensile Izod Impact Tensile Elongation ASTM D790 Strength @ Izod Impact Stress @ @ Break Flexural 23? C. (ft- Strength @ Example # Yield (MPa) (%) Modulus (MPa) lb/in) ?30? C. (ft-lb/in) 9 (control) 54.5 9.7 1923.6 9.51 3.05 10 58.9 25.7 1950.9 12.6 3.21 11 (control) 56.7 13.9 2053.6 12.8 2.49 12 56.8 28.4 2058.9 16.6 2.95

(20) TABLE 6 shows the composition of nylon 6-6 containing 30% glass fibers along with commercial available grafted maleic anhydride copolymers Fusabond? N493 (PE-g-MAh) and Royaltuf? 485 (EPDM-g-MAh) also known as impact modifier along with olefin-maleic anhydride copolymer (E-60).

(21) TABLE-US-00006 TABLE 6 Virgin Glass Example # Nylon-6,6 Fibers E-60 PE-g-MAh EPDM-g-MAh 13 (control) 62.5% 30% 7.5% 14 62.0% 30% 0.5% 7.5% 15 (control) 62.5% 30% 7.5% 16 62.0% 30% 0.5% 7.5%

(22) The Examples 14 and 16 containing E-60 in TABLE 7 are compared to their respective controls without E-60 (Example 13 and 15). It is believed that E-60 is acting as an interfacial agent between nylon, glass fiber and impact modifiers to yield improvements in all the mechanical properties including low temperature impact resistance.

(23) TABLE-US-00007 TABLE 7 ASTM D256 ASTM D638 Izod Impact Izod Impact Tensile Stress Tensile ASTM D790 Strength @ Strength @ @ Yield Elongation @ Flexural 23? C. ?30? C. Example # (MPa) Break (%) Modulus (MPa) (ft-lb/in) (ft-lb/in) 13 146.0 5.13 6808.9 2.91 2.02 (control) 14 149.7 5.33 6667.3 3.36 2.09 15 149.8 4.99 6768.3 2.93 2.06 (control) 16 149.8 5.09 7262.9 3.15 2.34
Preparation of Compositions with Recycled and Virgin Polyamide Using the Master Batch Approach

(24) Also described herein are compositions prepared using a master batch approach, which typically consists of two steps. In Step 1, the master batch is prepared by combining the olefin-maleic anhydride copolymer with an elastomeric material and in Step 2, the master batch is then let down or further compounded into a polyamide. In either of step 1 or 2, additional components may be included in the compositions.

(25) Step 1General Compounded Master Batch Preparation

(26) In addition to the above, compositions of this invention were prepared using the master batch approach. TABLE 8 shows the composition of each masterbatch (MB) MB-1, MB-2 and MB-3; processing was carried out using a counter-rotating inter-meshing twin screw extruder (Berstorff 25 mm.) with the temperature profile of 140, 150, 155, 155, 155, 155, 155, 170? C. resulting into strands that were cooled in a water bath and pelletized. TABLE 8 also shows composition masterbatch MB-4, compounding of which was carried out in two step process using a counter-rotating inter-meshing twin screw extruder (Berstorff 52 mm.). In each step the ratio of ZeMac? E-60 powder to the amine end-capped Nylon-6 (Ultramid? B24 NO2) was varied to get consistent feeding and avoid any severe reaction with amine end-capped Nylon-6. In both steps, the same temperature profile was used 150, 200, 230, 230, 200, 200, 200, 200, 200, 230? C. and the strands were cooled in a water bath and pelletized. A two-feeder system was used to feed the hopper for the compounding. The additives (e.g. stabilizer, anti-oxidant, optionally lubricant powders) are pre-mixed with olefin-maleic anhydride copolymers and fed through one feeder while carrier resin and other pellets described herein was fed through the other. The resulting pellets were dried for 12 hours at 70? C. to remove retained moisture. The formulations used for producing master batches with olefin-maleic anhydride copolymers are shown in TABLE 8.

(27) TABLE-US-00008 TABLE 8 Materials MB-1 MB-2 MB-3 MB-4 Optema TC141 25.0 25.0 Lotryl 28BA175 45.0 Ultramid? B24 N02 75.0 Amplify? GR216 50 ZeMac? E60 25.0 10.0 25.0 25.0 Cuprous iodide (CuI) 0.20 0.20 0.20 Potassium iodide (KI) 1.80 1.80 1.80 BNX? 1098.sup.1 2.00 2.00 2.00 Benefos? 1680.sup.2 6.00 6.00 6.00 Acrawax? C.sup.3 5.00 5.00 20.0 Polybond? 3200 12.50 DOW? LLDPE DNDB-1077 NT 7 22.50 *MB = Master batch Materials .sup.1N,N-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)] .sup.2Tris(2,4-di-tert-butylphenyl)phosphite .sup.3N,N Ethylene bis-stearamide
Step 2ACompounding Formulation of Master Batch and Elastomer with Recycled Polyamide-6

(28) The master batch MB-1 and MB-2 formulations shown in TABLE 8 were further compounded in second step in a counter-rotating inter-meshing twin screw extruder (Coperion ZSK-40) with recycled Polyamide-6 using the temperature settings of 230, 240, 240, 240, 240, 250, 250, 250, 250, 250, 245, 240? C. Both sets of formulations are shown in TABLE 9.

(29) TABLE-US-00009 TABLE 9 Recycled Examples Nylon-6 MB1 MB2 PE-g-MAh 17 (control) 100.0% 18 (control) 90.00% 10% 19 90.00% 2.50% 7.5% 20 95.00% 5.00% 21 93.75% 6.25%

(30) Tensile, flexural and Izod impact strength were measured using the methods listed in TABLE 1. The mechanical tests were carried out after drying the compounded pellets for 12 hours at 70? C. to remove retained moisture; the samples were used as molded after conditioning the test specimen as described in the ASTM protocol. Water absorption tests were carried after drying to equilibration to ensure that all the absorbed water is between 0.01%-0.3% dryness levels.

(31) TABLE 10 shows the tensile, flexural and notched Izod impact strength at room temperature for compounded recycled Polyamide-6. In general, the elastomers are known to enhance impact strength but decrease stiffness.

(32) TABLE-US-00010 TABLE 10 ASTM D638 ASTM D256 Tensile ASTM D790 Izod Impact Stress @ Tensile Flexural Strength Yield Elongation @ Modulus @ 23? C. Example # (MPa) Break (%) (MPa) (ft-lb/in) 17 (control) 63.60 17.21 2640.0 1.30 18 (control) 55.62 12.60 1966.7 7.73 19 58.70 61.59 2300.8 14.5 20 64.03 40.62 2366.8 2.87 21 62.23 45.83 2376.3 4.30

(33) The results shown in TABLE 10 for Example 18 (control), recycled Polyamide-6, compounded with the maleic anhydride-grafted elastomer (Fusabond? N493), shows improved Izod impact strength compared to the composition of control sample shown in Example 17 (control). However, both tensile and flex properties are lower. Even the tensile elongation is lower. Combining the master batch prepared with an elastomer as the carrier resin, such as that in Example 19, results in high impact strength and improved tensile strength, elongation and flexural modulus. Surprisingly, a small amount of master batch, 2.5 weight %, in combination with the elastomer at 7.5 weight % (Example 11) not only produces double the impact strength when compared to using toughener alone at the same overall weight % (Example 19) but produces impact strength comparable to that obtained from a composition containing a good commercial impact modifier at 20-25 weight %.

(34) The results obtained with the formulations in Examples 20 and 21 demonstrate that Izod impact strength is more than double when compared with the Examples 17 (control). Although the impact strength is not as high as when the elastomer is used alone or in combination with the master batch nevertheless overall there is an improvement in tensile strength and impact strength which is still very desirable for many applications.

(35) Step 2BCompounding Formulation of Master Batch and Elastomer with Virgin Polyamide-6 and Polyamide-6,6

(36) The compounded master batch MB-2 and MB-3 shown in TABLE 8 were re-compounded in second step in a counter-rotating inter-meshing twin screw extruder (Coperion ZSK-40) with virgin Polyamide-6 using the temperature settings of 230, 240, 240, 240, 240, 250, 250, 250, 250, 250, 245, 240? C. The formulations are shown in TABLE 11.

(37) TABLE-US-00011 TABLE 11 Virgin Example # Nylon-6 MB-2 MB-3 PE-g-MAh EPDM-g-MAh 22 85.0% 15.00% (control) 23 87.5% 6.25% 6.25% 24 85.0% 2.50% 12.50% 25 87.0% 2.50% 10.50% 26 75.0% 25.00% (control) 27 77.4% 5.60% 17.00% 28 85.0% 15.00% (control) 29 87.5% 6.25% 6.25% 30 85.0% 2.50% 12.50% 31 87.0% 2.50% 10.50% 32 75.0% 25.00% (control) 33 77.4% 5.60% 17.00%

(38) TABLE 12 shows the mechanical properties of control samples (Examples 22, 26, 28 and 32) containing two different commercial impact modifiers used at 15% and 25% levels in virgin Polyamide-6. As a result of masterbatch addition in Examples 23-25, 27, 29-31 and 32 shows moderate increase or retained impact resistance with significant increase in tensile strength, elongation and flexural modulus compared to their respective control samples. The resulting Polyamide-6 would be considered to be superior to commonly known super-tough nylon-6.

(39) TABLE-US-00012 TABLE 12 ASTM D638 Tensile ASTM D790 ASTM D256 Stress Tensile Flexural Izod Impact @ Yield Elongation @ Modulus Strength @ Example # (MPa) Break (%) (MPa) 23? C. (ft-lb/in) 22 (control) 51.3 10.2 1837.1 13.3 23 55.5 32.8 2008.1 14.2 24 56.3 43.9 2191.9 14.3 25 56.1 21.7 2011.6 13.2 26 (control) 39.1 18.1 1468.3 13.4 27 49.0 69.9 1905.1 17.7 28 (control) 49.6 23.5 1870.6 14.4 29 60.9 21.5 2415.7 14.8 30 53.0 66.7 1942.7 16.1 31 61.9 49.9 2384.4 15.3 32 (control) 38.3 35.6 1570.9 18.4 33 46.8 67.7 1909.3 19.3

(40) TABLE 13 shows the composition of virgin Polyamide-6,6 compounded with impact modifier and masterbatches using similar equipment as virgin Polyamide-6, however a different temperature profile of 243, 254, 262, 268, 274, 281, 280, 276, 271, 274? C. was used.

(41) TABLE-US-00013 TABLE 13 Virgin PE-g- EPDM- Example # Nylon-6,6 MB-2 MB-3 MB-4 MAh g-MAh 34 85.0% 15.0% (control) 35 87.5% 6.00% 6.5% 36 85.0% 2.40% 12.5% 37 85.0% 2.40% 12.5% 38 85.0% 15.0% (control) 39 87.5% 6.00% 6.5% 40 85.1% 2.40% 12.5% 41 87.1% 2.40% 10.5% 42 75.0% 25.0% (control) 43 75.0% 2.00% 23.0%

(42) TABLE 14 shows the mechanical properties of compounded compositions of TABLE 13. The virgin Polyamide-6,6 in the presence of masterbatch of olefin-maleic anhydride copolymer shows very similar trend of impact resistance improvement and other mechanical property enhancements as obtained in virgin Polyamide-6 (TABLE 12). Only exception is Example 35, where the impact resistance slightly goes down compared to its control (Example 34); however other mechanical properties are significantly improved. In other examples, compared to controls samples (Example 34 & 38), Examples 36 and 40 shows highly pronounced impact resistance enhancements in the presence of MB-3 when used in combination of either type of impact modifiers (Fusabond and Royaltuf).

(43) TABLE-US-00014 TABLE 14 ASTM ASTM D638 D790 ASTM D256 Tensile Tensile Flexural Izod Impact Stress @ Elongation Modulus Strength @ Example # Yield (MPa) @ Break (%) (MPa) 23? C. (ft-lb/in) 34 (control) 53.0 19.1 1945.2 11.3 35 62.2 27.5 2186.8 11.4 36 58.9 28.2 2145.3 14.8 37 60.3 23.7 2147.5 12.6 38 (control) 53.2 29.2 2069.0 12.5 39 64.7 26.1 2278.3 11.0 40 58.7 31.0 2111.1 15.6 41 61.7 27.9 2188.8 12.5 42 (control) 39.4 53.2 1469.0 19.1 43 44.9 42.2 1583.4 19.4

(44) As can be seen for control Examples 44, 49 and 52, shown in TABLE 15, the presence of an elastomer or an impact modifier generally results in a lower heat deflection/heat distortion temperature (HDT). The processes and compositions described herein surprisingly enhance the HDT even of virgin Nylonsthat are compounded with an elastomer or an impact modifier. TABLE 15 shows the composition and effect of ZeMac? E-60 and its masterbatches on HDT of virgin Nylon-6 and Nylon-66 in the presence of elastomer or an impact modifier.

(45) TABLE-US-00015 TABLE 15 ASTM Virgin D648 Virgin Nylon- PE-g- EPDM- HDT @ Example # Nylon-6 6,6 MAh g-MAh E-60 MB-2 MB-3 MB-4 66 psi (? C.) 44 (control) 85.00% 15.0% 148.8 45 86.87% 12.5% 0.625% 157.8 46 87.50% 6.25% 6.25% 153.3 47 85.10% 12.5% 2.4% 153.3 48 87.10% 10.5% 2.4% 155.3 49 (control) 85.00% 15.0% 145.9 50 86.87% 12.5% 0.625% 161.9 51 87.10% 10.5% 2.4% 157.7 52 (control) 85.00% 15.0% 187.6 53 86.90% 12.5% 0.60% 203.4 54 87.25% 6.25% 6.50% 214.0 55 85.10% 12.5% 2.4% 213.7 56 85.10% 12.5% 2.4% 206.9

(46) Examples 45-48, 50-51 and 53-56 in TABLE 15 show enhanced HDT values when compared to their respective control samples. Some of the compositions shown in TABLE 15 are similar to those shown in TABLES 11 and 13 except examples 45, 48, 50, 51, 53 and 56. The Examples in TABLE 15 which are similar to TABLES 11 and 13 containing masterbatches and impact modifiers not only show higher values of impact resistance but also show enhanced mechanical and thermal properties.

(47) Preparation of Articles with Composition

(48) The compositions of the present invention herein may be formed into articles using methods known to those skilled in the art. Illustrative examples include injection molding, blow molding, extrusion, and the like. The Polyamide-6 compositions of TABLE 11 were injection molded into various shapes such as dog bone and plaque. The molding was carried out using the following equipment and process conditions: i. Vandorn Intelect 110T injection molding press equipped with a standard single screw having diameter of 35 mm, an L/D ratio equal 20/1; ii. a barrel temperature between 225-250? C. with increasing profile; iii. a nozzle temperature of 238? C.; iv. a mold temperature of 83? C.; v. a mold for ASTM D638 Type I for tensile bars; vi. a mold with plaque dimension of 4.25 in?4.25 in?0.125 in; vii. a screw rotation speed of 100 RPM; viii. injection at speed 1-1.5 in/sec; ix. a specific injection pressure of 2300 psi and hold pressure of 800 psi; x. a hold time of 8-10 sec.

(49) While several illustrative embodiments of methods for production of polyamide compositions with high values of impact resistance, mechanical properties, thermal properties and methods for use of the compositions into articles have been described herein, the embodiments are merely offered by way of non-limiting examples of the invention described herein. Many variations and modifications of the embodiments described herein will be apparent in light of the disclosure. It is therefore to be understood that changes and modifications may be made by one of skill in the art, and equivalents may be substituted for elements thereof, without departing from the scope of the invention.

(50) Further, in describing representative embodiments, the disclosure may have presented a method and/or process as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. It will be appreciated that other sequences of steps may be possible. Therefore, the particular order of the steps disclosed herein should not be construed as limitations on the claims. In addition, the claims directed to a method and/or process should not be limited to the performance of their steps in the order written, and it will be readily appreciated that the sequences may be varied and still remain within the spirit and scope of the present invention.