Compositions, methods and articles produced by compounding polyamides with olefin-maleic anhydride polymers

Description

[0001] Polyamide is a polymer containing amide repeating units. These polymers can be both naturally occurring, e.g. proteins such as wool and silk, and may be produced artificially by gradual polymerization, e.g. nylons, aramids and sodium poly (aspartate). Today, polyamides are widely used in textiles, cars, carpets and sportswear because of their exceptional durability and strength.

[0002] One of the subsets of polyamides, nylons, is one of the most frequently formed subsets of synthetic polymers. Nylons are typically condensation copolymers formed by reacting dicarboxylic acids with diamines or by opening the ring of lactams. Various nylon polymers can be made by regulating the number of carbon atoms. Conventional nomenclature for these various nylons and polyamides includes diamine first and diacid designation second. Therefore, the most commercially popular variant of nylon, nylon 6-6, has six carbon donated by diamine and six carbon donated by diamine, and nylon 6-12 would have six carbon donated by diamine and twelve carbon donated by diacid Unlike nylon 6-6, nylon-6 is a homopolymer formed by ring opening polymerization. An example of this is nylon-6 produced by the polymerization of caprolactam. As each variant has a different chemical structure, the physical properties of the nylons differ in terms of impact resistance, tensile strength, flexibility, breaking strength, melting point, color fastness, and other properties.

[0003] Polymers of olefins with maleic anhydride (OMAP) result from the copolymerization of maleic anhydride with olefinic monomers. Examples of such olefins include ethylene, propylene, isobutylene, 1-butene, octene, butadiene, styrene, isoprene, hexene, long chain alkenes (e.g. dodekene, dodekene-1, tetradecene) and the like. Some of these olefins are derived from natural gas and / or crude oil, while others are derived from natural substances or biosynthesis. Examples of such copolymers include, but are not limited to, ethylene maleic anhydride, propylene maleic anhydride, isobutylene maleic anhydride copolymers, and terpolymers such as ethylene propylene maieic anhydride terpolymer.

[0004] It will be appreciated that products made from polyamides are subjected to considerable stresses during manufacture and processing, and that a method of making nylons or other polyamides with increased durability would be appreciated in the art, and that certain nylon formulations with increased durability would be appreciated. much appreciated in this area.

[0005] EP0693532 describes recycled polyamide compositions for use in blow molding, WO 1990007556 describes nylon blow molding compositions, and US 3,673,277 describes a thermosetting resin of polyamide and a copolymer of a polycarboxylic acid and an olefin.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] FIG. 1 Shows the reduction in viscosity at high shear rates resulting from mixing nylon (e.g., nylon-6) with EMA.

DESCRIPTION

[0007] The disclosure of the present use also provides various methods of making polyamide compounds with ethylene maleic anhydride (EMA) copolymers as described herein. Specifically, at least one embodiment of the present disclosure relates to methods of reacting nylon-like materials with ethylene maleic anhydride copolymers as described herein. At least one embodiment of the present disclosure includes processing methods such as extrusion mixing using equipment known to one skilled in the art. In the plastics industry, blending is a process that combines one or more polymers with one or more additives to produce plastic compounds in one or more steps. The raw materials can be granules, powders, and / or liquids, but the product is usually in the form of granules, for use in other plastic forming methods such as extrusion and injection molding. Machine sizes range from small laboratory machines to the largest extruders in the industry, reaching up to 20 tons per hour. Typically, twin screw extruders are preferred because they give better mixing at lower melting points. Most of them have screws and barrels composed of smaller segments (mixing, conveying, venting and adding additives) so that the design and addition order of each ingredient in the formulation can be changed and meet production and product requirements. Other equipment such as single screw extruders, oscillating screw extrusion, continuous mixers, Banbury mixers, and planetary extruders can also be used for joining. Additional ingredients for mixing and / or blending (viscosity modifiers, additive carriers, and the like) and processing parameters such as each zone temperature, feed rates, residence time, and screw speed may be modified by one skilled in the art for each application . The method of making polyamide compounds according to at least one embodiment of this application results in a mixed polymer with improved properties and performance such as increased tensile strength, impact strength, creep resistance and resistance to antifreeze degradation caused by hydrolysis of the compound formed by the reaction of the polyamide with olein-malein anhydride polymer.

[0008] In accordance with at least one embodiment of the method for making the conjugated polyamides of the present disclosure, the method comprises the step of combining the polyamide with an ethylene maleic anhydride copolymer as described therein in a twin screw extruder or other processing method as set forth in the preceding paragraph. Such granulate is then processed by a plastic processing method such as injection molding, blown or film casting, sheet extrusion, thermoforming or blow molding to a finished product such as a bottle, molded part, film, sheet, fabric, thread, fiber, e.t.c.

[0009] Another embodiment comprises directly extruding said reaction mixture into a finished article, such as thread, fiber, film, sheet and molded part.

[0010] In preparing the compounds of the present disclosure, the polyamide can be any suitable polyamide as described herein. For example, in the exemplary example, the polyamide made could be nylon, such as nylon-6 or nylon 6-6. Moreover, the polyamides used in at least one embodiment of the method of making a composite polyamide can be aliphatic, al, and cyclic and aromatic polyamides, such as one or more nylon 6-12, nylon 4-6, nylon 9, nylon 10, nylon 6-9, nylon 11, nylon 12, nylon 5-10, nylonmeta-xylenediamine (nylon-MXD6), Kevlar® (DuPont), Nomex® (DuPont), Ixef® (Solvay Advanced Polymers), Trogamid® (Evonik Degussa) and Amodel® ( Solvay Advanced Polymers). In addition, in the process for producing a composite polyamide, an alternating ethylene maleic copolymer (EMA) is used in the treatment process at a 1: 1 mole ratio of ethylene to maleic anhydride. In yet another embodiment, non-alternating copolymers or random copolymers can be used.

[0011] The olefin maleic anhydride described herein for reaction with a polyamide has a weight average molecular weight ranging from 10,000 to 1 million. For example, according to at least one embodiment, the selected EMA may have a molecular weight of about 60,000, such as that sold under the trademark ZeMac® E-60 (E60), or the selected EMA may have a molecular weight of about 400,000, such as the one sold under the trademark ZeMac® E-400 (Vertellus Specialties Inc.) (E400). In addition, EMA may be used in an embodiment of the composite polyamide manufacturing process at a concentration from about 0.01% to about 20.0% w / w; about 0.02% to about 0.5%; about 0.05% to about 7.0% w / w; about 0.1% to about 5.0% w / w; or about 0.5% to about 3.0% w / w.

[0012] According to at least one optional embodiment, the stabilizer pack is added to a formula (formulation), including additives used individually or in combination with each other. In accordance with one such embodiment, the additives may include phenolic antioxidants, phosphites, copper iodide (CuI), potassium iodide (KI), and / or other stabilizers. Optionally, the stabilizer kit may contain about 0.01% to about 5.0% w / w of the total reaction mixture; about 0.1% to about 2.0% w / w; or about 0.5% to 1.0% w / w.

[0013] A number of illustrative embodiments of the invention are described in the following clauses:

1. A method of making a composite polyamide comprising essentially from:

forming a polyamide reaction mixture by contacting the polyamide with a 1: 1 (molar ratio) ethylene maleic anhydride copolymer, where the 1: 1 (molar ratio) ethylene maleic copolymer has a weight average molecular weight ranging from 10,000 to 1 000,000; and combining the polyamide reaction mixture at processing temperature and optionally contacting the polyamide reaction mixture with the glass fibers.

2. The method defined in clause 1 wherein the polyamide is nylon.

3. A method as defined in clause 1, wherein the polyamide is selected from the group consisting of nylon-6, nylon 6-6, nylon-6 copolymer and nylon 6-6, nylon-9, nylon-10, nylon-11, nylon-12, nylon 6-10, aromatic polyamides, elastomeric polyamides, and mixtures thereof.

4. A process as defined in clause 1 wherein the polyamide is selected from the group consisting of nylon-6, nylon 6-6, nylon-6 and nylon 6-6 copolymer, and mixtures thereof.

5. The process as defined in clause 1 wherein the olefin-maleic anhydride copolymer has a concentration of from about 0.01% to about 0.5%, about 0.5% to about 1.0%, about 1.0% to about 1.5%. % or 1.5% to about 3.0% w / w.

6. The method as defined in clause 1 wherein the processing temperature is about 230 ° C to about 300 ° C.

7. A method as defined in clause 1, wherein the step of forming the polyamide reaction mixture further comprises the step of mixing the polyamide with the glass fibers.

8. The method as defined in clause 1, wherein the glass fiber concentration is from about 0.1% to about 30%.

9. The process as defined in clause 1, wherein the step of forming the polyamide reaction mixture further comprises the step of contacting the polyamide with one or more stabilizing agents.

10. A method as defined in clause 9, wherein each of the one or more stabilizing agents is independently selected from the group consisting of copper iodide, potassium iodide, tris (2,4-di-tert-butylphenyl) phosphite and N, N'-hexane-1. , 6-diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenyl opropionam and d)).

11. A method as defined in clause 9 wherein each of the one or more stabilizing agents independently has a concentration from about 0.01% to about 1.0% w / w.

12. A composite polyamide produced by the method in clause 1.

13. A composite polyamide of clause 12, where the polyamide is selected from the group consisting of nylon-6, nylon 6-6, nylon-6 copolymer and nylon 6-6, nylon-9, nylon-10, nylon-11, nylon-12, nylon 6-10, aromatic polyamides, elastomeric polyamides, and mixtures thereof.

14. The composite polyamide of clause 12, wherein the polyamide is selected from the group consisting of nylon-6, nylon 6-6, nylon-6 and nylon 6-6 copolymer, and mixtures thereof.

15. The composite polyamide of clause 12, wherein the polyamide is selected from the group consisting of nylon-6 and nylon 6-6.

16. The composite polyamide of Clause 12 wherein ethylene maleic anhydride has a concentration from about 0.01% to about 0.5%, about 0.5% to about 1.0%, about 1.0% to about 1.5% or 1.5% to about 3.0% w / w.

17. The polyamide composite of clause 12, wherein the processing temperature is about 230 ° C to about 300 ° C.

18. The composite polyamide of clause 12, wherein the polyamide reaction mixture further comprises glass fiber.

19. The composite polyamide of clause 18, wherein the glass fiber concentration is from about 0.1% to about 30%.

20. The composite polyamide of clause 12, wherein the polyamide reaction mixture further comprises one or more stabilizing agents.

21. A complex polyamide of clause 20 wherein the one or more stabilizing agents are independently selected from the group consisting of copper iodide, potassium iodide, tris (2,4-di-tertbutylphenyl) phosphite, and N, N'-hexane-1,6-diylbis ( 3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)).

21. The composite polyamide of clause 21, wherein each of the one or more stabilizing agents independently has a concentration from about 0.01% w / w. to about 1.0% w / w.

22. The composite polyamide of clause 12 wherein the ethylene maleic anhydride copolymer has a molecular weight of from about 60,000 to about 400,000.

23. A composite polyamide according to any one of the preceding clauses, wherein the polyamide is recycled nylon.

[0014] Moreover, in accordance with additional embodiments, UV stabilizers and absorbents, halogenated or non-halogenated flame retardant additives; enhancers such as mineral or fibers, fabrics, wandering fibers, pipes and yarns made of glass, carbon, graphite, cellulose and other natural materials; and / or high melting aromatic polymers (sometimes referred to as aramids) are included in the reaction mixture. Plasticizers, spreads, rheology modifiers, friction modifiers and other additives known to those skilled in the art can also optionally be added to the mixture depending on application requirements.

[0015] According to at least one step of forming the polyamide reaction mixture, the combination of the components may be accomplished with any type of suitable extruder such as a single or twin screw extruder, or a suitable extruder used in conjunction with the mixer.

[0016] When carrying out the bonding step in an embodiment of the method for making a composite polyamide of the present disclosure, the first temperature may be any temperature sufficient to melt the polyamide and facilitate bonding of the polyamide to the EMA. In an embodiment with nylon-6, the temperature settings on the extruder and the processing temperature may be about 230 ° C to about 300 ° C. In other embodiments, the temperature settings and fusion temperature may be from about 230 ° C to about 260 ° C, or from about 220 ° C to 260 ° C. In the case of nylon 6-6 amine for reaction.

R- (CH₂-CH₂-MAh)_n-Rf ethylene male anhydride polymer, this temperature may be from 250 ° C to 310 ° C or from 240 ° C to 280 ° C. However, for higher melting point polyamides such as the Nomex® polymer, such processing temperatures are possible in the range of 280 ° C to 380 ° C. For elastomeric polyamides such as nylon-9, nylon-10, nylon-6.10, nylon-11, and nylon-12, the range can be much smaller, from 150 ° C to 250 ° C. It is recognized that the upper fusion temperature may be related to the temperature at which degradation of the nylon bonding becomes significant, the lower value may be related to the melting or softening point of the nylon.

[0017] Without wishing to be bound by theory, it is believed that nylons (also called polyamides) require the presence of a free amino group in order for it to react with the anhydride groups of the olefin-maleic anhydride copolymer (see formula below). Pictorially, Ultramid B3S, which has free amino groups and is not end-terminated, reacts, while Ultramid B27, which is end-capped, has no free groups

H.₂N-CH₂-CH₂-CH₂-CH₂-CH₂-CO (HN-CH₂-CH₂OH₂-CH₂-CH₂-WHAT)_m-R 'nylon-6 mH polyamide₂About v

CO-NH-CH₂-CH2-CH₂-CH₂-CH₂-CO (HN-CH₂-CH₂-CH₂-CH₂-CH₂-WHAT)_m-R '

AND

R- (CH₂-CH₂-CH-CH)_n-R

CO-NH-CH₂-CH₂-CH₂-CH₂-CH₂-CO (HN-CH₂-CH₂-CH₂-CH₂-CH₂-WHAT)_m-R 'polyamide compound

[0018] In at least one embodiment of the polyamide bonding method, the step of forming the polyamide reaction mixture may further include the step of contacting the polyamide with glass fibers. The introduction of the glass fiber may take place before or after the polyamide is combined with the EMA. The glass fiber may have a concentration of about 0.1% to about 60%; about 10% to about 50%. Moreover, in an exemplary embodiment of the present disclosure, the glass fiber may have a grade and size used for bonding to nylons.

[0019] According to other exemplary embodiments, other enhancers may be combined with polyamide, including carbon tubes, mica, talc, calcium carbonate, wollastonite, carbon fibers, Keviar® fibers, nanoparticles made of clay, and other materials. Other embodiments include fabrics, roving fibers, pipes, and yarns made of glass, cellulose, and other natural materials, carbon, graphite, high melting point aromatic polymers (sometimes referred to as aramids), and ceramics. A specific example is Kevlar® fibers 12 microns in diameter and 0.5 inch long. Another example is a biaxially oriented glass fiber fabric such as the VECTORPLY ™ E-LTM 3610.

[0020] The exemplary embodiment of a method for producing a composite polyamide may also include the step of injection molding the polyamide. Optionally, the polyamide can be combined with the EMA directly during injection molding.

[0021] As a result of producing a composite polyamide according to an embodiment of the method set forth in the present disclosure, it has been found that the treated polyamide (ie, composite polyamide) exhibits increased impact strength and / or increased tensile strength as compared to untreated polyamide. The enhanced impact strength may be at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 28%, at least about 30%, at least about

33%, at least about 35%, at least about 40%, or at least about 50%, more than unformulated polyamide.

[0022] In accordance with at least one embodiment of a composite polyamide of the present disclosure, a composite polyamide formed by a method of combining a polyamide with an EMA is disclosed. In addition, the polyamide optionally can be nylon-6 or nylon-66, and the EMA has a molecular weight from about 60,000 to about 400,000. The polyamide also can be nylon-9, nylon-12, nylon-11, nylon 4-6 or any of the following. the polyamides mentioned herein. In another illustrative embodiment, the polyamide linked to the EMA in any of the embodiments described herein may be recycled nylon.

[0023] The recycled nylon / polyamide can contain many different types of materials of varying quality from various fields. Recycled polyamide can come from either post-industrial or post-production sources, or a combination of both. An example of a high quality secondary nylon is undyed nylon, which is of sufficient molecular weight for injection molding. Another example of recycled nylon is polyamide / nylon, the so-called "Off-spec" or "unprimed" that does not meet the specifications for an intended use, or is an intermediate material that is produced when switching between production of one grade of nylon and another grade of nylon. This type of nylon secondary material is priced around 2-5% below the price of primed nylon to around 25% below the price of primed nylon depending on market conditions. Much of the lower quality secondary nylon currently available is landfilled. Examples of lower quality secondary nylon sources are the textile or hosiery industry. Secondary fishing nets are another source. Much of this lower quality material is low viscosity nylon which normally cannot be used for injection molding without the modification as described herein. Automotive recycled nylon is typically black and cannot be used for applications other than black. Recycled nylon may also contain one or more non-polyamide polymers. In one example, carpet scrap typically contains 80-85% polyamide, the remainder of the material being polyester, polypropylene and some polyurethane. Due to poor mechanical performance, carpet waste is usually not reused and ends up in landfills. Depending on the performance and quality of the material, the prices of polyamides vary. By combining these types of recovered polyamides with the EMA copolymers as described herein, these materials can be used in higher value-added applications.

[0024] The reacted or composite polyamide can be incorporated into any product where enhanced properties are more desirable than unformulated polyamide. In an exemplary embodiment, the composite polyamide can be incorporated into any of carpet fibers, garments, airbags, tires, ropes, conveyor belts, hoses, luggage, molded products (such as auto parts, weapon frames, electrical parts, and tool holders), products. personal care (such as toothbrushes), medical devices and surgical products, food packaging film, oil-resistant seals defense and space products and bulletproof materials.

[0025] The cross-linked compositions of the present disclosure prepared by using relatively higher levels of olein-maleic anhydride (OMAP) polymer in a polyamide matrix are applied to nylon in die casting or thermal lamination. To achieve these goals, the OMAP ratio is in the range of about 10% to about 50% w / w. or about 10% to about 20%. The use of a cross-linked composition of this variation is optionally processed by methods conventionally used in thermosetting polymers, some of which employ a fabric reinforcement made of glass fibers. Such polymers may be useful in metal replacement applications (e.g., mechanical parts, medical devices, etc.) for transportation applications. Other applications include the defense industry and aviation. The olefin-maleic anhydride polymer may be an alternating polymer of ethylene maleic anhydride in a 1: 1 ratio.

[0026] As used herein, the term "combination generally refers to a method that combines one or more polymers with one or more additives to produce plastic compounds in one or more steps." The materials to be mixed can be granules, powders and / or liquids. Typically the product is in the form of granules for use in other plastic forming methods such as extrusion and injection molding.

METHODS AND EXAMPLES

MATERIALS

[0027] Polyamide 6 (Ultramid ™ B3S grade) and polyamide 6.6 (Ultramid ™ A34 grade) both of the first (primed) quality from BASF were used as received and also made of a secondary polyamide 6. Care was taken to keep all species dry. The examples used a 1: 1 alternating copolymer of ethylene maleic anhydride ZeMac ™ E60 (E60) from Vertellus Specialties Inc. having a weight average molecular weight (Mw) of 60,000. The examples used a 1: 1 alternating copolymer of ethylene maleic anhydride of ZeMac ™ E400 (E400) from Vertellus Specialties Inc. with a weight average molecular weight (Mw) of 400,000. A stabilizing package consisting of 0.09% potassium iodide (KI), 0.01% copper iodide (Cul), 0.4% Irgafos ™ 168 (phosphite stabilizer) and 0 , 5% Irganox ™ 1098 (phenolic hindered antioxidant) was used with all pooled (composite) samples.

PREPARATION OF TOTAL COMPOUND POLYAMIDE

[0028] Polyamide composite granulate with E60 or E400 was prepared in a counter-rotating twin-screw extruder (Bertstroff 25mm, 32D). Samples of polyamide-6 and polyamide-6 secondary were used at temperature settings of 235, 245, 255, 245, 240, 240, 240, 240 ° C, while samples of polyamide-6.6 were combined using temperature settings of 250, 265, 275 , 270, 270, 270, 270, 280 ° C. For the GF reinforced runs, glass fiber, at a 30% loading level, was fed via a side feeder.

GENERAL TEST METHODS

[0029] Tensile, bend, notch Izod impact and flow index tests were performed using ASTM Standard Methods D-638, D-790, D-256 and D-1238 at 23 ° C, respectively. Charpy impact strength was measured by the method ISO-179-2 / 2 at room temperature (23 ° C) and -30 ° C. Heat deflection / deformation temperature was measured using ASTM method D-648. These mechanical and thermal tests were performed without additional drying, the samples were used as molded after conditioning the test sample according to the ASTM protocol. Water absorption tests were performed after drying to equilibrium to ensure that all absorbed water was removed and all samples were dry. The percentage increase in the amount of absorbed water was determined after 24, 48 and 72 hours.

PRIMATED POLYAMIDE-6

[0030] Polyamide-6 was blended with a 1% ethylene maleic anhydride copolymer with and without 30% glass fiber. Tensile tests, elongation, notch Izod impact force of the obtained combined materials are shown in TABLE 1 below.

TABLE 1

<td>Preparation</td><td>Nylon-6 + no additive</td><td>Nylon-6 + 1% E6O</td><td>Nylon-6 + 30% glass fiber + no additive</td><td>Nylon-6 + 30% glass fiber + 1% E6O</td>

<td>Tensile strength under stress (MPa)</td><td> 50</td><td> 70,5</td><td> 69</td><td> 79</td>

<td>Elongation at break when stretching (%)</td><td> 5,9</td><td> 8,0</td><td> 4,9</td><td> 9,2</td>

<td>Elongation in tension at yield (%)</td><td> 5,2</td><td> 7,9</td><td> 4,9</td><td> 8,8</td>

<td>Modulus of elasticity (MPa)</td><td> 1150</td><td> 1200</td><td> 2250</td><td> 2400</td>

<td>Izod test (ftIb./in.)</td><td> 1,30</td><td> 1,55</td><td> 1,50</td><td> 2,00</td>

<td>Izod's test (J / m.)</td><td> 69</td><td> 83</td><td> 80</td><td> 107</td>

[0031] The results of the tensile, elongation and Izod crimp impact tests shown in TABLE 1 show that the alternating copolymer increases all three properties with and without 30% glass fiber. Typically, as the tensile strength increases in most plastics with some kind of modification, the elongation decreases, and vice versa. It has been found that combining polyamide with EMA increases both the tensile strength and the elongation. These observations show that the basic structure of at least part of the polyamide is modified into a highly branched structure with a very high molecular weight, making the composite polyamide stronger and harder

[0032] During bonding, an increase in both viscosity and torque is observed. When a polyamide grade without end groups was used, no increase in viscosity or in mechanical properties was observed. This indicates that no amidation can occur unless there are amine end groups on the polyamide. It was also observed that cross-linking can occur at high EMA loads (&gt; 10%) and the resulting mixed (composite) material does not flow. The use of other materials that have one reactive group, i.e. one anhydride (e.g. maleic anhydride grafted polyethylene) or a modifier with one reactive group at each end shows only a slight increase in viscosity and a slight increase in mechanical properties compared to the use of EMA copolymers (unique structures with thousands of reactive groups on each molecular chain) disclosed herein.

This increase in viscosity also reduces the melt flow of polyamide-6 as shown in TABLE 2.

TABLE 2

Melt index at 235 ° C and Ikg (g / lOmin)

Addition

<td>not combined - REF</td><td> 9,7</td>

<td>0.1% E60</td><td> 4,3</td>

<td>0.3% E60</td><td> 1,7</td>

<td>0.5% E60</td><td> 1,0</td>

POLYAMIDE-6.6 PRIMATED

[0033] It was observed during joining that the polyamide 6.6 produced greater viscosity build-up and torque at the same EMA loading levels. This can be attributed in part to the higher temperature at which polyamide-6.6 is processed compared to polyamide-6, but also because polyamide-6,6 typically has amine end groups at both ends. As with polyamide-6, the mechanical properties of polyamide-6,6 are also improved while the melt index decreases. In addition, we observed an increase in heat deflection temperature under pressure as shown in TABLE 3 below.

TABLE 3

<td>Addition</td><td>Melt index at 275 ° C and 5 kg (g / 10 min)</td><td>Temp, deflection under pressure in ° C at 1.82 Mpa (264 psi)</td>

<td>not combined REF</td><td> 142,05</td><td> 59,6</td>

<td>no additives REF</td><td> 29,06</td><td> 70,5</td>

(continued)

<td>Addition</td><td>Melt index at 275 ° C and 5 kg (g / 10 min)</td><td>Temp, deflection under pressure in ° C at 1.82 Mpa (264 psi)</td>

<td>0.1% E60</td><td> 21,12</td><td> 74,1</td>

<td>0.3% E60</td><td> 8,98</td><td> 71,0</td>

<td>0.5% E60</td><td> 2,27</td><td> 71,3</td>

RECYCLING NYLON-6

[0034] The recycled polyamide used in this study is predominantly nylon-6 from an industrial source. Due to the presence of some nylons-6,6 in this recycled polyamide, the melt index is lower than usually expected from a recycled stream with polyamide-6 alone. It generated less torque during bonding than the corresponding nylon-6 primed. Without wishing to be bound by theory, it is believed that the lower torque is due to the expected degradation caused by the secondary heat genesis of the secondary nylon-6 compared to primed nylon-6. TABLE 4 shows the decrease in melt index in the recycled polyamide combined with E60. This decrease in melt index is believed to be due to chain elongation and resulting branching. The resulting thinning shear allowed for excellent injection molding, contrary to what would be expected from the fractional melt flow rates obtained when forming the ASTM test specimens.

_________ TABLE 4______________________ Melt Flow Rate (ASTM D-1238) 235 ° C w / 1 kg (g / 10 min)

Addition

<td>none E60 REF</td><td> 13</td>

<td>no additives REF</td><td> 6,2</td>

<td>0.1% E60</td><td> 1,17</td>

<td>0.3% E60</td><td> 0,80</td>

<td>0.5% E60</td><td> 0,44</td>

<td>1% E60</td><td> 0,5</td>

<td>3% E60</td><td> 1,6</td>

<td>Nylon-6 Primed</td><td> 9,65</td>

[0035] The tensile strength of the injection molded specimens was measured according to the ASTM D638 protocol. The results are shown in TABLE 5. Various commercial grades of primed polyamide-6 differ slightly in tensile strength as indicated in the safety data sheets provided by the supplier.

[0036] As can be seen from the data in TABLE 5, after the reactive combination of a secondary polyamide with an ethylene maleic anhydride alternating copolymer to form a composite secondary polyamide, the tensile strength values ​​agree with or approach the range of values ​​of primed types of polyamides (75 to 85 MPa) ). Other properties of the composite secondary polyamide have also been improved. TABLE 6 shows the properties of the modulus of elasticity of the secondary polyamide as a function of the addition of small loads of the same alternating ethylene-maleic anhydride copolymer.

[0037] This increase in the elastic modulus of the composite secondary polyamide corresponds to or exceeds the similar range of the modulus of elasticity of different grades of primed polyamide 6 available from various suppliers. The increase in bending strength at break is also observed for the composite secondary polyamide as shown in TABLE 6. The values ​​for both the modulus of elasticity and the flexural strength show that the values ​​increase as a function of the amount of alternating copolymer added from 0.1 to 0.5%. The values ​​do not appear to increase further as the percentage of E60 added is further increased.

TABLE 5 Increase of tensile strength of secondary polyamide as a result of reaction E60.

<td>Composite Recycled Polyamide</td><td colspan="2">MECHANICAL PROPERTIES AT TENSION (ASTM D638)</td>

<td>Addition</td><td>Tensile strength under stress at yield (MPa)</td><td>Elongation at break (%)</td>

<td>none E60 REF</td><td> 61,1</td><td> 19,47</td>

<td>no additives REF</td><td> 78,2</td><td> 18,24</td>

(continued)

<td>Composite Recycled Polyamide</td><td colspan="2">MECHANICAL PROPERTIES AT TENSION (ASTM D638)</td>

<td>Addition</td><td>Tensile strength under stress at yield (MPa)</td><td>Elongation at break (%)</td>

<td>0.1% E60</td><td> 78,5</td><td> 12,66</td>

<td>0.3% E60</td><td> 80,2</td><td> 17,58</td>

<td>0.5% E60</td><td> 79,5</td><td> 12,79</td>

<td>1% E6O</td><td> 82,0</td><td> 29,17</td>

<td>3% E60</td><td> 80,4</td><td> 15,91</td>

<td>Nylon-6 Primed</td><td> 83,6</td><td> 12,41</td>

TABLE 6 Increase in the modulus of elasticity and strength of secondary polyamide as a result of the _________________________________ reaction E60, __________________________________

<td rowspan="2">Addition</td><td colspan="2">FLEX ASTM D790</td>

<td>Comp. Module (Mpa)</td><td>Strength of stress, at break (Mpa)</td>

<td>none E60 REF</td><td> 2385</td><td> 77,2</td>

<td>no additives REF</td><td> 2632</td><td> 102,5</td>

<td>0.1% E60</td><td> 2689</td><td> 105,7</td>

<td>0.3% E60</td><td> 2749</td><td> 114,0</td>

<td>0.5% E60</td><td> 3016</td><td> 121,1</td>

<td>1% E6O</td><td> 2867</td><td> 110,8</td>

<td>3% E60</td><td> 2866</td><td> 113,3</td>

<td>Nylon-6 Primed</td><td> 2 796</td><td> 113,8</td>

[0038] The impact strength measured by the Izod method for the composite secondary polyamide was measured according to the ASTM D256 protocol. The results measured at room temperature (23 ° C) and -30 ° C are shown in TABLE No. 7. The results show an increase as a function of the alternating copolymer addition level both at room temperature and at -30 ° C. It is surprising, however, that the values ​​measured at low temperature are surprisingly higher than the values ​​measured at room temperature and are higher than the values ​​measured for the primed nylon-6.

[0039] The Charpy impact strength at 23 ° C and -30 ° C is shown in TABLE 8. The increases in Charpy impact strength were observed compared to that in the absence of alternating copolymer addition. However, the increase is not progressive at 0.5% and 23 ° C loading levels. Compared to the values ​​for primed polyamide, they are exceeded at 23 ° C for all three loads, but only by 0.5% at -30 ° C.

TABLE 7 Increase in impact strength measured by the Izod method of secondary polyamide combined with E60 measured at 23 ° C and -30 ° C.

<td>Addition</td><td>IZOD IMPACT (</td><td>(ft-lb / in) ASTM D256</td>

<td></td><td>at 23 ° C</td><td>at -30 ° C</td>

<td>none E60 REF</td><td> 0,52</td><td>0.42 (CB)</td>

<td>no additives REF</td><td> 0,87</td><td>0.45 (CB)</td>

<td>0.1% E60</td><td> 0,96</td><td>1.01 (CB)</td>

<td>0.3% E60</td><td> 1,05</td><td>1.30 (CB)</td>

<td>0.5% E60</td><td> 1,32</td><td>1.39 (CB)</td>

<td>Nylon-6 Primed</td><td>1.33 (CB)</td><td>0.46 (CB)</td>

TABLE 8 Increase in Charpy impact strength of secondary polyamide combined with E60 measured at room temperature (23 ° C) and -30 ° C.

<td rowspan="2">Addition</td><td colspan="2">CHARP RESISTANCE ISO-179-2 / 2 (KJ / m²)</td>

<td>at 23 ° C</td><td>at -30 ° C</td>

<td>none E60 REF</td><td> 33,8</td><td> 24,7</td>

<td>no additives REF</td><td> 46,9</td><td> 19,9</td>

<td>0.1% E60</td><td> 40,3</td><td> 23,7</td>

<td>0.3% E60</td><td> 48,4</td><td> 29,2</td>

<td>0.5% E60</td><td> 40,1</td><td> 39,4</td>

<td>Nylon-6 Primed</td><td> 32,2</td><td> 22,3</td>

[0040] It should be noted that the addition of polar E60 as an additive may result in increased water absorption in the combined polyamide samples. Water absorption measurements were performed after the sample had dried to equilibrium to make sure it was dry. The amount of water absorbed was determined after 24, 48 and 72 hours. As shown in TABLE No. 9, only a slight increase in water absorption was observed in the samples of the polyamide combined with the E60 copolymer.

TABLE 9

<td rowspan="2">Addition</td><td colspan="3">WATER ABSORPTION (%)</td>

<td>after 24h</td><td>after 48h</td><td>after 72h</td>

<td>none E60 REF</td><td> 1,03</td><td> 1,48</td><td> 1,79</td>

<td>no additives REF</td><td> 1,02</td><td> 1,42</td><td> 1,77</td>

<td>0.1% E60</td><td> 1,28</td><td> 1,69</td><td> 2,24</td>

<td>0.3% E60</td><td> 0,88</td><td> 1,32</td><td> 1,56</td>

<td>0.5% E60</td><td> 0,69</td><td> 1,10</td><td> 1,97</td>

<td>1% E60</td><td> 1,09</td><td> 1,50</td><td> 1,8</td>

<td>3% E60</td><td> 0,87</td><td> 1,38</td><td> 1,82</td>

EXAMPLE

[0041] In determining the effect of ethylene maleic anhydride (EMA) copolymers on nylon-6 and nylon 6-6, both types of nylon were combined with 30% glass fibers, 1.4% EMA, and a stabilizer pack containing a combination of compounds disclosed in TABLE 2 . The composite nylon granulate was then formed into ASTM test specimens and the following properties were tested: Notched Izod Impact, Izod Not Notched Impact, as well as strength properties, fracture strain and yield stress. The fusion of the nylon, glass fiber, EMA and stabilizer pack was done on a twin screw extruder with all ingredients added to the hopper. In accordance with the exemplary embodiment, the melting point of the nylon mixture was 260 ° C for the nylon-6.6 compounds and 240 ° C for the nylon-6 compounds. The pictorial results of the analysis of the properties of composite nylon versus untreated nylon are shown in TABLE 10. The grade of glass fiber used in this mixture was a 10 µm diameter, 4.5 mm long high performance E-glass chopped glass fiber typically used for extrusion with layout polyamide resin.

TABLE 10

<td colspan="4">Comparison of the Physical Properties of Nylon Compounds</td>

<td>Preparation (all with 30% E glass *)</td><td>Nylon-6 no EMA REF</td><td>Nylon-6 w / E400</td><td>Nylon-6 w / E60</td>

<td>Tensile strength (MPa)</td><td> 176,3</td><td> 162,1</td><td> 160,9</td>

(continued)

<td colspan="4">Comparison of the Physical Properties of Nylon Compounds</td>

<td>Preparation (all with 30% E glass *)</td><td>Nylon-6 no EMA REF</td><td>Nylon-6 w / E400</td><td>Nylon-6 w / E60</td>

<td>Elongation while stretching (%)</td><td> 3,70</td><td> 4,86</td><td> 5,50</td>

<td>Izod's test (ft-lb./in.)</td><td> 1,80</td><td> 1,62</td><td> 2,30</td>

<td>No notch Izod test (ft-lb./in.)</td><td> 20,5</td><td> 17,5</td><td> 23,1</td>

TABLE 11

<td colspan="2">Stabilizing Composition as a Function of Total Compound Mass</td>

<td>Relationship</td><td>% w / w up to the sum of 100%</td>

<td>Copper iodide</td><td> 0,01%</td>

<td>Potassium iodide</td><td> 0,09%</td>

<td>Irgafos 168 (phosphite)</td><td> 0,40%</td>

<td>Irganox 1098 (with phenolic obstacle)</td><td> 0,50%</td>

In each of the following TABLES 12-15, except the first entry, each polymer was combined with the stabilizing composition in TABLE 11

TABLE 12 - Nylon-6 Melt Flow Rate Index z

Recyclable at 235 ° C and Ikg (g / 10 min)

<td>Not connected REF</td><td>No extras REF</td><td>0.1% E60</td><td>0.3% E60</td><td>0.5% E60</td><td>1% E60</td><td>3% E60</td>

<td> 13,0</td><td> 6,2</td><td> 1,2</td><td> 0,8</td><td> 0,4</td><td> 0,5</td><td> 1,6</td>

TABLE 13 - Tensile Strength of Secondary Nylon-6 (MPa) *

<td>Not connected</td><td>No extras</td><td>0.1% E60</td><td>0.3% E60</td><td>0.5% E60</td><td>1% E60</td><td>3% E60</td>

<td> 61,1</td><td> 78,2</td><td> 78,5</td><td> 80,2</td><td> 79,5</td><td> 82,0</td><td> 80,4</td>

<td colspan="7">* Values ​​for Primed Nylon are in the range of approximately 65-71 MPa</td>

<td>tab:</td><td colspan="5">ELA 14 - Nylon-6 Secondary Modulus of Elasticity (Ml</td><td colspan="2">Bye) *</td>

<td>Not connected REF</td><td>Lack additives REF</td><td>0.1% E60</td><td>0.3% E60</td><td>0.5% E60</td><td>1% E60</td><td>3% E60</td><td>1% E400</td>

<td> 2385</td><td> 2632</td><td> 2689</td><td> 2749</td><td> 3016</td><td> 2867</td><td> 2866</td><td> 3000</td>

<td colspan="4">* Values ​​for Primed Nylon are in the eye range</td><td colspan="4">about 2600-2800 MPa</td>

TABLE 15 - Modulus of Elasticity at Break Secondary Nylon-6 (MPa) *

<td>Not connected REF</td><td>No REF additives</td><td>0.1% E60</td><td>0.3% E60</td><td>0.5% E60</td><td>1% E60</td><td>3% E60</td><td>1% E400</td>

<td> 77,24</td><td> 102,52</td><td> 105,70</td><td> 113,95</td><td> 121,09</td><td> 110,78</td><td> 113,3</td><td> 119,15</td>

<td colspan="8">* Values ​​for Primed Nylon are in the range of approximately 100-108 MPa</td>

<td rowspan="14">At 0.1% ZeMac E-60 in Primed Nylon 6-6 (BASF Ultramid A34), the composite polyamide shows improvements in several properties:</td><td>Specific Gravity</td><td>ASTM D792</td><td>(g / ml)</td><td> 1,14</td><td> 1,14</td><td rowspan="14">MFI - Melt Flow Index, FIDT - Thermal Deflection Temperature, NB - No Break, CB - Complete Break FIB - Half Break</td>

<td>MFI</td><td>ASTM D1238</td><td>275 ° C and 5Kg (g / 10 min)</td><td> 142,1</td><td>r - H. (No.</td>

<td>HDT</td><td>ASTM D648</td><td>264 psi (° C)</td><td> 59,6</td><td> 74,1</td>

<td rowspan="2">Love Charpy</td><td rowspan="2">ISO-179-2 / 2</td><td>-30 ° C (KJ / m^AND2)</td><td>33.6 (NB)</td><td>35.8 (NB)</td>

<td>Temp, room (KJ / m^AND2)</td><td>36.00 (NB)</td><td>35.0 (NB)</td>

<td rowspan="2">Uda Izod</td><td rowspan="2">ASTM D256</td><td>-30 ° C (ftIb / in)</td><td>0.48 (CB)</td><td>0.42 (CB)</td>

<td>Temp, room (ft-lb / in)</td><td>0.54 (CB)</td><td>1.07 (CB)</td>

<td rowspan="2">Flexure</td><td rowspan="2">ASTM D790</td><td>Stress at Break Break (MPa)</td><td> 100,8</td><td> 112,3</td>

<td>Modulus (MPa)</td><td> 2787</td><td> 2781</td>

<td rowspan="4">Mechanical properties in stretching</td><td rowspan="4">ASTM D638</td><td>Deformation At Break (%)</td><td> 33,6</td><td> 13,1</td>

<td>Stress At Break (MPa)</td><td> 56,9</td><td> 66,1</td>

<td>Strain at yield strength (MPa)</td><td> 75,4</td><td> 84,8</td>

<td>Modulus (MPa)</td><td> 2653</td><td> 2719</td>

<td colspan="2"></td><td>Addition</td><td>not combined REF</td><td>0.1% E60</td>

TABLE 17

<td colspan="10">Primed Nylon-6 (Ultramid B3S BASF) combined with E60 shows improvement</td>

<td rowspan="2">follow</td><td colspan="9">properties:</td>

<td colspan="2">Mechanical properties in stretching</td><td colspan="2">Flexure</td><td>Uda Izod</td><td colspan="2">Charpy Impact</td><td>HDT</td><td>MFI</td>

<td></td><td colspan="2">ASTM D638</td><td colspan="2">ASTM D790</td><td>ASTM D256</td><td colspan="2">ISO-179-2 / 2</td><td>AST M D648</td><td>AST M D123 8</td>

<td>Dodate k</td><td>Deformation at the yield point i (MPa)</td><td>Deformation At Break (%)</td><td>Modulus (MPa)</td><td>Stress At Break (MPa)</td><td>-30 ° C (ftIb / in)</td><td>23 ° C (KJ / m^AND2)</td><td>-30 ° C (KJ / m ^Λ2)</td><td>264 psi (° C)</td><td>235 ° C w / 1 kg (g / 10 min)</td>

<td>not connected REF</td><td> 83,6</td><td> 12,4</td><td> 2796, 1</td><td> 113,8</td><td>0.46 (CB)</td><td>32.2 (NB)</td><td>22.3 (CB)</td><td> 62,1</td><td> 9,65</td>

<td>0.1% E60</td><td> 78,4</td><td> 11,4</td><td> 2680, 2</td><td> 105,4</td><td>0.38 (CB)</td><td>42.9 (NB)</td><td>(CB)</td><td> 59,1</td><td> 4,34</td>

<td>0.3% E60</td><td> 78,8</td><td> 14,5</td><td> 2747, 6</td><td> 106,9</td><td>0.46 (CB)</td><td>44.6 (NB)</td><td></td><td> 55,3</td><td> 1,73</td>

<td>0.5% E60</td><td> 85,4</td><td> 15,0</td><td> 2992, 0</td><td> 121,3</td><td>0.61 (CB)</td><td>49.7 (NB)</td><td>23.9 (CB) 27.0 (CB)</td><td> 56,5</td><td> 0,97</td>

<td rowspan="7">in combination with 30% glass fiber and E60.</td><td>HDT</td><td>ASTM D648</td><td>264 psi (° C)</td><td> 198,8</td><td> 192,3</td>

<td rowspan="2">Charpy Impact</td><td rowspan="2">ISO-179-2 / 2</td><td>-30 ° C (KJ / m^AND2)</td><td>5.80 (CB)</td><td>7.62 (CB)</td>

<td>Temp, room (KJ / m^AND2)</td><td>6.24 (CB)</td><td>7.09 (CB)</td>

<td rowspan="2">Izod impact strength</td><td rowspan="2">ASTM D256</td><td>-30 ° C (ftIb / in)</td><td>(ao) lCo</td><td>0.73 (CB)</td>

<td>Temp, room (ftłb / in)</td><td>1.13 (CB)</td><td>1.13 (CB)</td>

<td rowspan="3">Flexure</td><td rowspan="3">ASTM D790</td><td>Strain At Yield Strength (MPa)</td><td> 24,6</td><td> 130,9</td>

<td>Stress At Break (MPa)</td><td> 112,6</td><td> 122,9</td>

<td rowspan="6">Properties of primed nylon-6 (Ultramid B3S by BASF)</td><td>Modulus (MPa)</td><td> 7263</td><td> 6744</td>

<td rowspan="4">Mechanical properties in stretching</td><td rowspan="4">ASTM D638</td><td>Strain At Break (%)</td><td> 3,17</td><td> 3,34</td>

<td>Stress At Break (MPa)</td><td> 78,6</td><td> 82,5</td>

<td>Strain At Yield Strength (MPa)</td><td> 78,8</td><td> 82,9</td>

<td>Modulus (MPa)</td><td> 5586</td><td> 5547</td>

<td></td><td></td><td>Addition</td><td>0.3% E60</td><td>0.5% E60</td>

<td rowspan="11">Properties of nylon 6,6 primed (Ultramid A-34 by BASF) with 30% glass fiber.</td><td rowspan="2">Charpy</td><td rowspan="2">ISO-179-2 / 2</td><td>AT OO</td><td>(KJ / m^AND2)</td><td>5.68 (CB)</td><td>6.82 (CB)</td>

<td>At o (No.</td><td>(KJ / m^AND2)</td><td>5.50 (CB)</td><td>6.79 (CB)</td>

<td rowspan="2">Charpy Impact</td><td rowspan="2">ASTM D256</td><td>uo O</td><td>(ftIb / in)</td><td>0.71 (CB)</td><td>0.67 (CB)</td>

<td>At o (No.</td><td>(ftIb / in)</td><td>0.94 (CB)</td><td>0.93 (CB)</td>

<td rowspan="2">Izod impact strength</td><td rowspan="2">ASTM D790</td><td>Strength Comp. Pisa Breakup</td><td>(MPa)</td><td> 140,6</td><td> 144,6</td>

<td>Module</td><td>(MPa)</td><td> 7471</td><td> 6873.</td>

<td rowspan="4">Mechanical Properties In Tension</td><td rowspan="4">ASTM D638</td><td>Tensile Strain (Elongation) At Break</td><td> (%)</td><td> 2,86</td><td> 3,36</td>

<td>Tensile Stress At Break</td><td>(MPa)</td><td> 97,7</td><td> 102,5</td>

<td>Tensile At Na Stress</td><td>(MPa)</td><td> 97,1</td><td> 102,8</td>

<td>Modulus of Elasticity</td><td>(MPa)</td><td> 6548</td><td> 5723</td>

<td colspan="2">30% GF in Nylon 6-6 (Ultramid A34)</td><td>Addition</td><td></td><td>0.3% E60</td><td>0.5% E60</td>

EXAMPLE

[0042] In accordance with this example, the effect of reacting the secondary nylon with various ethylene maleic anhydride (EMA) copolymers was evaluated. In accordance with at least one embodiment, the recycled nylon has been treated with an EMA as discussed in more detail below, and the reaction product has been evaluated for resistance to anti-freeze degradation due to hydrolysis and impact strength as compared to untreated recycled nylon. The results indicate that treating nylon and other polyamides with EMA can improve both the resistance to antifreeze degradation due to the hydrolysis properties and the impact strength of the composition compared to untreated polyamides.

The composite nylon-6 showed an increase in the impact force of the Izod notched specimens from 3 ft-lb / in for unprepared nylon-6 to 3.78 ft-lb / in and 4.72 ft-lb / in. In addition to increasing resistance to anti-freeze degradation due to hydrolysis and impact strength, the composite nylon is expected to exhibit an increase in breaking strength, a reduction in creep, and a reduction in the coefficient of linear thermal expansion.

EXAMPLE

[0044] The properties of various nylon-6 (PA6) blends (as shown in TABLE 20) were tested with and without an ethylene maleic anhydride (EMA) copolymer to determine the effect of treating nylon-6 with EMA on the physical properties of nylon6. For nylon-6 processing, the nylon-6 / ΕΜΑ blend was mixed in a co-rotating twin screw extruder (Leistritz, ZSE, 27HP, D = 40mm) and then injection molded with an injection molding machine (Cincinnati Milacron-Fanuc, Roboshot, 55USTON, 1.95or) for standard tensile and impact bars. The bonding conditions in which nylon-6 was mixed are shown in TABLE 21. Further, the injection molding conditions are shown in TABLE 22. Additionally, all of the nylon-6 was pre-dried at 85 ° C overnight before mixing. The properties of several nylon-6 blends with EMA are shown in TABLES 12-15.

TABLE 20

<td colspan="4">Nylon Blend Components</td>

<td>Blend</td><td>Content Polymer [phr]</td><td>Filler content [phr]</td><td>EMA content [phr]</td>

<td>Nylon-6</td><td> 100</td><td> 0</td><td> 0</td>

<td>Nylon-6 + EMA **</td><td> 100</td><td> 0</td><td> 10</td>

<td>Nylon-6 + EMA</td><td> 100</td><td> 0</td><td> 1</td>

<td>Nylon-6 + GF</td><td> 67</td><td> 33</td><td> 0</td>

<td>Nylon-6 + GF + EMA **</td><td> 70</td><td> 30</td><td> 10</td>

<td>Nylon-6 + GF + EMA *</td><td> 70</td><td> 30</td><td> 1</td>

TABLE 21 - PA6 Joining Conditions

<td></td><td>Temp. [° C]</td><td>RPM</td><td>Torque [%]</td><td>Pressure [psi]</td><td>Feed [%]</td>

<td>Nylon-6 + GF</td><td> 200-230-240</td><td> 50</td><td> 60</td><td> 80</td><td> 20</td>

<td>Nylon-6 + GF +</td><td> 200-230-240</td><td> 65</td><td> 30</td><td> 310</td><td> 20</td>

<td>EMA</td><td></td><td></td><td></td><td></td><td></td>

<td>Nylon-6 + EMA</td><td> 200-230-240</td><td> 65</td><td> 30</td><td> 350</td><td> 25</td>

<td>Nylon-6</td><td> 200-220-230</td><td> 50</td><td> 40</td><td> 30</td><td> 25</td>

TABLE 22

<td colspan="4">Injection Molding Conditions</td>

<td></td><td>Temp. Barrels [° F]</td><td>Temp. Molten Material [° F]</td><td>Cooling time [s]</td>

<td>Nylon-6 + GF</td><td> 440-465</td><td> 150</td><td> 30</td>

<td>Nylon-6 + GF + EMA</td><td> 440-465</td><td> 150</td><td> 30</td>

<td>Nylon-6 + EMA</td><td> 440-465</td><td> 150</td><td> 30</td>

(continued)

<td colspan="4">Injection Molding Conditions</td>

<td></td><td>Temp. Barrels [° F]</td><td>Temp. Molten Material [° F]</td><td>Cooling time [s]</td>

<td>Nylon-6</td><td> 440-465</td><td> 150</td><td> 30</td>

<td colspan="4">GF - glass fiber</td>

[0045] All specimens were tested for impact properties according to ASTM D256 with a 2 lb-ft pendulum and tensile strength properties according to ASTM D638 at a cross head speed of 50 mm / min. In determining these properties, the Modulus of Elasticity (as shown in TABLE 1) indicates the bending force. Note that as the results increase, the stiffness of the sample increases, and when the results are lower, the flexibility increases. As shown in TABLE 1, the strain at break was calculated as a percentage with high numbers indicating the extensibility before breaking the sample. The yield stress, shown in TABLE 1, was calculated for each sample, indicating the force at the apex before reduction. In other words, as the material stretches it requires more force to be stretched until it reaches the "neck" point where the specimen is thinned enough to require less tensile force. In general, care should be taken to ensure that fragile materials do not collapse. Moreover, as can be seen in TABLE 1, the yield strain is shown, denoting the percentage change in length, where a higher value means that the specimen must stretch before finally breaking. The specimens were finally tested for impact strength which is the force required to break the specimen. This is a high speed impact test where the higher the number the higher the impact force. Each of these tests was run 4-5 times and the average was saved.

EXAMPLE

[0046] 40 g of nylon-6 granules and 4 g of ZeMac® E-60 (E60) were mixed at room temperature in a Brabender laboratory mixer, preheated to 245 ° C until all the granules had melted and the mixture was well foamed. At ratios of 10% and greater than 10%, the ethylene maleic anhydride copolymer did not flow and appeared to cross-link the polyamide.

EXAMPLE

[0047] The formed tensile bars are immersed in the refrigerant (commercially available Prestone® Ready to Use Premixed Anti-freeze) at 125 ° C for 3000 hours (every 500 hours). One set of 5 samples for each formulation is removed from the test fluid at 500-hour intervals, washed with water, dry wiped and its strength properties are tested. The resistance to hydrolysis was demonstrated by comparing the tensile properties of the processed bars with the raw bars.

[0048] While various embodiments of methods for making the compositions and methods of using the compositions have been described in detail herein, the methods are not limited to the examples of the invention described herein. Many variations and modifications to the embodiments described herein will become apparent in light of the disclosure. It should therefore be understood that various changes and modifications may be made and that their substitutes may be replaced without departing from the scope of the invention. Indeed, this disclosure is not intended to be exhaustive or limit the scope of the invention. The scope of the invention is defined by the appended claims and their equivalents.

[0049] Moreover, by describing representative embodiments, the disclosure has been able to represent a method and / or process as a specific sequence of steps. However, to the extent that the method or process is not based on any particular order of steps given herein, it should not be limited to the particular sequence of the steps described. Note that other step sequences are possible. Therefore, the particular order of the steps disclosed herein should not be construed as limiting the claims. Moreover, the objections to the method and / or process should not be limited to performing the steps of the method or method in a recorded order.

[0050] It is therefore intended that the invention include, and that this description and appended claims will cover all modifications and variations apparent from this disclosure.