ARTICLES

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. provisional patent application no. 62/975820, filed February 13, 2020, and to European patent application no. 20178761.1, filed June 8, 2020, both of which are incorporated herein by reference.

FIELD OF THE INVENTION

The invention relates to polymeric ports having a bead free of parting lines and an undercut ratio of at least 10%. The invention further relates to polymeric port fabrications and articles including the polymeric ports.

BACKGROUND OF THE INVENTION

In many applications, such as automotive applications, ports are needed to transfer, via hoses, fluids between components. Traditional components including ports are generally made from metal and include a bead at the distal end of the port to help retain a tube inserted over the bead. The tube can be further secured to the port with a hose clamp or the like, to further aid against unintentional tube detachment.

However, metallic components are heavy and costly to manufacture. On the other hand, the need for light weighting is rapidly growing, especially in the transportation industry (e.g. automotive and aerospace). For example, in such industries, light weighting of components can lead to significantly increased efficiencies and reduced emissions. Accordingly, there is a need for polymeric components, including polymeric ports, to further advance light weighting efforts.

However, polymeric ports come with their own difficulties. In particular, because molds for injection molding of necessarily include distinct pieces (so that the part can be ejected after molding), the formed part necessarily has parting lines at the location where distinct pieces of the mold meet. At the bead, the parting line can damage the hose inserted over the bead, which can lead to fluid leaks and unintentional hose detachment. However, if there is no parting line the bead area, the bead can be damaged (e.g. deformed or cracked) and the circularity of the port compromised, as ejecting the part requires pulling the sleeve over the bead (there is no parting line to separate the mold at the bead). While incorporation of low performance polymeric material can address the issue of bead damage, the ports cannot be used in high performance applications requiring mechanical strength at elevated temperatures ( e.g . automotive applications).

SUMMARY OF INVENTION

In ones aspect, the invention is directed to 1. A polymeric port comprising a bead, free of a parting line, disposed at a distal end of the polymeric port, wherein the bead comprises a maximum outer bead diameter (“OD1”) and an inner bead diameter (“ID”), wherein ID is at leaset 20.5 mm; a shaft, disposed at a proximal end of the polymeric port and extending to the bead, wherein the shaft comprises an outer shaft diameter (120) that is less than OD1; a channel extending through the shaft and the bead; and an undercut ratio of at least 10%, preferably at least 10.5%. The undercut ratio is given by the formula 100*(OD1-OD2)/ID. The polymeric port comprises a polymeric material comprising: a tensile strength at break at least 25 MPa at 25° C; at an ejection temperature (“Te”), a tensile elongation of break of at least 8% and a tensile strength of at least 50 MPa; and a polymer comprising a Te-Tg > 20° C, a Tm-Te less than or equal to 150° C, and a Tm of at least 200° C, wherein Tg and Tm are, respectively, the glass transition temperature and the melting temperature of the polymer, wherein the tensile elongation at break and the tensile strength at break are measured according to ASTM D638.

In some embodiments, the polymer is selected from the group consisting of a polyamide, a polysulfone, a poly(aryl ether ketone) and a poly(arylene sulfide)s, preferably a polyamide. In some such embodiments, the polymer is a semi-aromatic polyamide comprising a recurring unit (RPA) formed from the polycondensation of: (i) a diamine selected from the group consisting of 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino- octane, 1,9-diaminononane, 2-methylpentamethylenediamine, 1,10-decanediamine, 1,11- diaminoundecane, 1,12-diaminododecane, 1,3-diaminocyclohexane, 1,4- diaminocyclohexane, l,3-bis(aminomethyl)cyclohexane, l,4-bis(aminomethyl)cyclohexane, bis(3-methyl-4-aminocyclohexyl)-methane, and 4,4'-methylene-bis-cyclohexylamine; and (ii) a dicarboxylic acid selected from the group consisting of terephthalic acid and isophthalic acid.

In another aspect, the invention is directed to a method of making a polymeric port, the method comprising reinserting a core into the channel to reform the bead (104, 316), wherein prior to the reinserting, the polymeric port is formed by: (i) injecting molten polymeric material into a mold comprising the core and a sleeve, wherein the core forms the channel and the sleeve forms the outer surface of the polymeric port; (ii) cooling the polymeric material; (iii) removing the core from the channel; and (iv) removing the sleeve from the port by sliding it over the bead; and wherein the sleeve is a unitary structure where it forms the outer surface of the bead during the injecting.

In a further aspect, the invention is directed to an article comprising a polymeric port.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 displays schematic representations of a perspective view (a) and cross-sectional views (b) and (c), of a polymeric port.

Fig. 2 is a schematic representation of a cross-sectional view (a) and distal view (b) of a polymeric port having a parting line.

Fig. 3 is a schematic depiction of a fabrication method for polymeric ports.

DETAILED DESCRIPTION OF THE INVENTION

Described herein are polymeric ports including a shaft, disposed at the proximal end of the port, extending to a bead, disposed at the distal end of the port, and a channel extending through the shaft and bead (through the port). The bead is free of parting lines. In some embodiments, the polymeric port is free of parting lines. Furthermore, the ports have an undercut ratio of at least 10% and have beads having an inner diameter, at the location of the maximum outer diameter of the bead, (“inner bead diameter”) of at least 20.5 mm. Also described herein are fabrication methods for the polymeric ports as well as articles including the polymeric ports.

As described above, polymeric ports having beads can cause damage to hoses inserted over the bead. While the parting line can be eliminated from the bead area of the port having a unitary mold at that location, the bead can be damaged as it is slid through the sleeve of the mold during ejection (the mold is unitary at the bead location so it cannot be separated there). The use of low performance polymers can address bead damage, however, it limits the application settings of the polymeric ports. In particular, low performance polymers have, a melting temperature (“Tm”) of less than 200° C and a tensile strength of less than 25 MPa at 25° C (“room temperature”). To obtain polymeric ports that can be used in high temperature applications ( e.g . automotive), polymeric materials including high performance polymers (Tm is at least 200° C and the tensile strength is at least 25 MPa at room temperature) are highly desirable. However, because of their increased mechanical strength, the issue of bead damage during ejection is exacerbated. It was found, however, that bead damage can be mitigated by limiting the inner diameter of the port under the bead in conjunction with appropriate selection of high performance polymeric material. In general, when the inner bead diameter is less than or equal to 20 mm, a polymeric port having an undercut ratio of from 10% to 12% can, in general, be ejected, with negligible damage, from a unitary portion of a mold. The undercut ratio is 100 times the difference between the maximum outer diameter of the bead and the outer diameter port shaft, divided by the inner bead diameter, as explained in detail below. For ports having inner bead diameters of greater than 20 mm, polymeric ports having beads free of parting lines and an undercut ratio of at least 10% cannot be formed by methods known in the art, without damage to the bead during ejection.

It was found that with a particular combination of polymeric material, incorporating a high performance polymer, and port fabrication process, polymeric ports having beads free of parting lines; an inner bead diameter of greater than 20.5 mm, and an undercut ratio of at least 10% could be formed, without undesirable damage to the bead during ejection. The polymeric ports described herein are made from a polymeric material including a tensile strength at break at least 25 MPa at 25° C; at an ejection temperature (“Te”), a tensile elongation of break of at least 8% and a tensile strength of at least 50 MPa. The polymeric material further includes a polymer comprising a Te-Tg > 20° C, a Tm-Te less than or equal to 150° C, and a Tm of at least 200° C, wherein Tg and Tm are, respectively, the glass transition temperature and the melting temperature of the polymer. Te refers to the temperature of the polymeric port when it is subjected to the mold removal process (ejection). For the polymeric materials described herein, Te is selected such that Te-Tg > 20° C and Tm- Te is less than or equal to 150° C, 140° C, 130° C, or 120° C, where Tg and Tm are, respectively, the glass transition temperature and melting temperature of the polymer in the polymer. Furthermore, the fabrication process includes a step of reinserting the core into the channel of the port, to reform the bead subsequent to removing the sleeve (sliding the sleeve over the bead).

In some embodiments, the polymeric ports have an inner bead diameter of at least 21 mm, at least 21.5 mm or at least 22 mm. In some embodiments, the polymeric ports have an inner diameter of at no more than 30 mm, no more than 28 mm, no more than 26 mm, or no more than 24 mm. In some embodiments, the polymeric ports have inner bead diameters of from 20.5 mm to 30 mm, 20.5 mm to 28 mm, 20.5 mm to 26 mm, 20.5 mm to 24 mm, from 21 mm to 30 mm, 21 mm to 28 mm, 21 mm to 26 mm, 21 mm to 24 mm, from 21.5 mm to 30 mm, from 21.5 mm to 28 mm, from 21.5 mm to 26 mm, from 21.5 mm to 24 mm, from 22 mm to 30 mm, from 22 mm to 28 mm, from 22 mm to 26 mm, or from 22 mm to 24 mm. In some embodiments, the polymeric ports have an undercut ratio of at least 10.5%, at least 11%, at least 11.5% or at least 12%. In some embodiments, the polymeric ports have an undercut ratio of no more than 18%, no more than 17%, or no more than 16%. In some embodiments, the polymeric ports have an undercut ratio of from 10% to 18%, from 10% to 17%, from 10% to 16%, from 10.5% to 18%, from 10.5% to 17%, from 10.5% to 16%, from 11.0% to 18%, from 11.0% to 17%, from 11.0% to 16%, from 11.5% to 18%, from 11.5% to 17%, from 11.5% to 16%, from 12% to 18%, from 12% to 17%, from 12% to 16%.

As used herein, “substantially” means that the indicated property or value does not vary by more than 2%, preferably 1%. For example, a shaft that is substantially cylindrical has an outer diameter that does not vary more than 2%, preferably 1%, from the average diameter along the shaft.

Polymeric Ports

Figs. 1 and 2 show an embodiment of a polymeric port. Fig. 1 displays schematic representations of a perspective view (a) and cross-sectional views (b) and (c), of a polymeric port. Cross-sectional view (b) and (c) are identical, though showing different numbering for clarity. Referring to Fig. 1, polymeric port 100 comprises shaft 102, bead 104, and channel 106 extending through polymeric port 100 (extending through shaft 102 and bead 104). Shaft 102 is disposed at the proximal end of port 100 and extends to bead 104, which is disposed at the distal end of port 100. Channel 106 forms distal opening 108 and proximal opening 110 at, respectively, the distal end and proximal end of polymeric port 100. Long axis 112 extends through the center of channel 106. For clarity, any reference to the diameter of polymeric port, or a component thereof, refers to the diameter in a cross-section taken in a plane perpendicular to long axis, unless explicitly noted otherwise. For example, reference to the diameter of polymeric port 100, or a component thereof, refers to the diameter in a cross- section taken in plane perpendicular to long axis 112, unless explicitly noted otherwise.

Channel 106 is a fluid communication channel. Fluid can pass through channel 106, from distal opening 108 through proximal opening 110 or from proximal opening 110 through distal opening 108. In the former case, polymeric port 100 is an inlet, and in the latter case, polymeric port 100 is an outlet. Of course, polymeric port 100 can be an inlet as well as an outlet, allowing fluid flow through channel 106 in both directions.

Channel 106 extends through polymeric port 100 and, therefore, through shaft 102 and bead 104. In some embodiments, channel 106 is substantially cylindrical in shaft 102, which has inner diameter 114 (outer diameter of channel 106 in shaft 102, inner diameter of shaft 102). In some embodiments, however, channel 106 in shaft 102 can be a truncated cone (also called a tapered cylinder). For example, in some embodiments, the diameter of channel 106 at the distal end of shaft 102 can be larger than the diameter of proximal opening 110, and the diameter of channel 106 can change linearly along long axis 112 from the distal end of shaft 102 to proximal opening 110. As another example, in alternative embodiments, the diameter of channel 106 at the distal end of shaft 102 can be smaller than the diameter of proximal opening 110, and the diameter of channel 106 at the distal end of shaft 102 can change linearly along long axis 112 from the distal end of shaft 102 to proximal opening 110. In preferred embodiments, channel 106 is substantially cylindrical in shaft 102. The person of ordinary skill in the art will recognize that because channel 106 extends through polymeric port 100, the diameter of channel 106 defines the inner diameter of shaft 102 and bead 104 at any point along polymeric port 100.

Channel 106 in bead 104 has a circular cross section in a plane perpendicular to long axis 112. In some embodiments, the diameter of channel 106 in bead 104 varies along at least a portion of long axis 112. In some such embodiments, the diameter of channel 106 in the bead 104 is greater than or equal to the diameter of channel 106 in shaft 102. Put another way, the diameter of channel 106 in shaft 102 at any point along long axis 112 is less than or equal to the diameter of channel 106 in bead 104 at any point along long axis 112. In alternative embodiments, the diameter of channel 106 in bead 104 is substantially cylindrical. In one such embodiment, the diameter of channel 106 in bead 104 and the diameter of channel 106 in shaft 102 are substantially the same. Channel 106 has inner bead diameter 114, at location 116 along long axis 112 where bead 112 has maximum outer bead diameter 118. As noted above, inner bead diameter 114 is at least 20.5 mm. The ranges for inner bead diameter 114 are within the ranges given above.

Along long axis 112, shaft 102 is substantially cylindrical (has an outer surface that is substantially cylindrical), while the outer diameter of bead 104 varies. Shaft 102 has a substantially constant, circular outer shaft diameter 120 along long axis 112 and, therefore, forms a substantially cylindrical external surface. The outer diameter of bead 104 is substantially circular, but changes along long axis 122. Accordingly, shaft 102 and bead 104 are both symmetric, relative to any plane containing long axis 112 and any plane perpendicular to long axis 112. Bead 104 has maximum outer bead diameter 118. Maximum outer bead diameter 118 is greater than outer shaft diameter 120. The difference between maximum outer bead diameter 118 and outer shaft diameter 120 helps to retain hoses that are disposed over bead 104, guarding against unintentional hose detachment and fluid leakage. Preferably, the difference between maximum outer bead diameter 118 and outer shaft diameter 120 is 2 mm to 4 mm. Maximum outer bead diameter 118 is displaced away from distal opening 108 and towards proximal opening 110. In the region along long axis 112, between maximum outer bead diameter 118 to distal opening 108, the outer diameter of bead 104 is less than maximum outer bead diameter 118. In the region along long axis 112, between maximum outer bead diameter 118 to the distal end of shaft 102, the outer diameter of bead 104 is less than or equal to maximum outer bead diameter 118, preferably less than maximum diameter 118. In some embodiments, the outer diameter of bead 104 at distal opening 108 is substantially the same as the outer diameter of shaft 102. Additionally, or alternatively, in some embodiments, along long axis 112, the outer diameter of bead 102 in the region from maximum outer bead diameter 118 to the proximal end of shaft 102 is substantially the same. In such embodiments, the person of ordinary skill in the art will recognize that the outer diameter of polymeric port 100 changes discontinuously between bead 104 and shaft 102.

Notably, bead 104 is free of parting lines. That is, the outer surface of bead 104 is free of discontinuities, for example, formed by injection molding polymeric material into a mold that is composed of multiple distinct, pieces at the portion where the bead is formed. In general, molds are not a unitary piece. More particularly, because the part must eventually be ejected (removed) from the mold, the mold is made of two or more pieces. The molds are made from metal. Accordingly, due to the elevated mold temperatures during injection molding, the mold must have a non-zero tolerance where the distinct pieces meet. As a result, the molded part ( e.g . the polymeric port) has a parting line where two distinct pieces of the mold the meet. That is to say, the molten polymeric material can flow into gaps between the two distinct pieces of the mold and form a parting line. Fig. 2 is a schematic representation of a cross-sectional view (a) and distal view (b) of a polymeric port having a parting line. Referring to Fig. 2, polymeric port 200 includes shaft 202, bead 204 and long axis 206. As explained above, parting lines 208, 210 can be formed where two halves of a mold meet (e.g. wherein the sleeve forming the out surface of polymeric port 200 meet). The parting line (e.g. parting lines 208, 210) can be sharp, and can damage hoses disposed over the bead, leading to fluid leaks from the tube and unintentional tube detachment from port 100. The risk to hose damage is further increased when hose clamps are used to further secure a hose to a polymeric port. On the other hand, bead 104 is free of parting lines. Preferably, the external surface of bead 104 and shaft 102 (e.g. the external surface of polymeric port 100) are both free of parting lines. Most preferably, polymeric port 100 is free of parting lines. The fabrication of polymeric ports and port components free of parting lines is described in detail below. In some embodiments, outer surface of bead 104 has a maximum step of no more than 0.5 mm, no more than 0.1 mm, or no more than 0.01 mm, as measured using a contact profilometer.

As noted above, the polymeric ports have an undercut ratio of at least 10%. The undercut ratio of polymeric port 100 is given by 100*(maximum outer bead diameter 118 — outer shaft diameter 120)/(inner bead diameter 114). As noted above, inner diameter 114 is the inner diameter of bead 104 at the location of maximum outer bead diameter 118 along long axis 112, as indicated by line 118. The ranges for the undercut ratio of polymeric port 102 is within the ranges given above.

Fabrication Methods

The fabrication method includes reinserting a core to reform the bead. The polymeric ports are injection molded, which involves using a mold, including a core and sleeve. The core is inserted into the sleeve and the port is formed by injecting molten polymeric material into the space between the core and the sleeve. Once cooled to the ejection temperature, the part (including the port) is ejected. Ejecting the part involves removing the core and, subsequently, the sleeve. The removal of the sleeve can negatively impact the bead morphology, for example, by reducing the undercut ratio and introducing undesirably amounts of eccentricity into the bead ( e.g . making the bead undesirably less circular and more elliptical). By reinserting the core subsequent to sleeve removal while the polymeric material is still at elevated temperatures, the undesirable effects of sleeve removal are mitigated.

Figs. 4 is a schematic representation of a fabrication method for forming a part including a port. Referring to panels (a) to (e), mold 300 includes core 302 and sleeve 304 and part 310 includes port 306 and body 308. Sleeve 304 and part 310 are shown in a cross- sectional view, in a plane containing the long axis 312 of port 306. Referring to panel (a), core 302 is inserted into sleeve 304. In general, the mold is made from metal, such as aluminum or steel, or alloys of either. Notably, in region where sleeve 304 forms the outer surface of bead 316 during injection molding (where it is in contact with the outer surface of bead 316 during injection molding), it is a unitary structure. Put another way, in the region where sleeve 304 forms the outer surface of bead 316 during injection molding, sleeve 304 is a unitary structure (e.g. at the aforementioned location, sleeve 304 is not formed by brining distinct pieces of sleeve 304 together). As such, bead 316 is free of parting lines. Preferably, sleeve 204 is a unitary structure where it forms port 206 during injection molding. In such an embodiment, the external surface of port 206 is free of parting lines. Most preferably, both sleeve 204 and bead 316 are unitary structures where they form bead 316 during injection molding.

Prior to injecting molten polymeric material into the space between core 302 and sleeve 304, core 302 and sleeve 304 are heated to Te, as described above. In some embodiments, Te is from 110°C to 170°C, from 120°C to 160°C or from 130°C to 150° C. Referring to panel (b), once mold 300 is at Te, molten polymeric material (the temperature of the polymeric material is above Tm) is injected into the space between core 302 and sleeve 304. In general, the molten polymeric material is at a temperature of from Tm + 10° C to Tm + 30° C during injection. Core 302 is hollow and forms channel 314 of port 306, channel 302 extending through bead 316 and shaft 318). The outer diameter of core 302 forms the inner diameter of polymeric port 206 (inner diameter of bead 316 and shaft 318). Sleeve 304 forms the outer surface of polymeric port 306. When the polymeric material cools to Te (or to a temperature that is no more than 10° C above Te), part 310 is ejected from mold 300. Tg and Tm can be determined according to ASTM D3418. For clarity, where the polymeric material includes a plurality of polymers, Tg and Tm refer to the polymer with the highest Tg and the polymer with the highest Tm, respectively.

Referring to panel (b) of Fig. 3, Because the polymeric ports described herein have beads free of parting lines, releasing part 310 from mold 300 involves sliding core 302 and sleeve 304 away from port 306 to release port 306 from mold 300. Port 306 is released from the mold by first removing core 302 from port 306 by pulling core 302 away from port 306 in a direction along the long axis 312 of port 306, as indicated by the arrow on core 302. Referring to panel (c), subsequently, sleeve 304 is removed from port 306 by pulling sleeve 304 away from port 306 in a direction along the long axis 312 of port 306 and over the external surface of port 306, as indicated by the arrows on sleeve 304. In the process, bead 316 is flattened when sleeve 304 is pulled over bead 312, as shown in exemplary regions 320, 322, which are designated by circles. For clarity, the entirety of bead 312 is flattened. When port 306 is released from mold 300, as shown in panel (d), bead 316 is generally deformed, and channel 314 of port 306 can be undesirably ovoid along bead 316. To mitigate the issue of bead deformation, core 302 is then reinserted into port 306 to reform bead 316 and channel 314, as shown in panel (e). Subsequently, core 302 is again removed from port 306, as explained above.. The person of ordinary skill in the art will recognized that the arrows in Fig. 4, representing the removal of the mold 300 components from the part 310, are relative. That is to say, mold 300 components are displaced away from part 310 during ejection. Put another way, mold 300 components can be moved relative to part 310, part 310 can be moved relative to mold 300 components, or a combination of both.

The Polymeric Material

The polymeric port is formed from a polymeric material including polymer and, optionally, other components. In general, the polymer of the polymeric material is not particularly limited. The polymeric material has a tensile strength at break at least 25 MPa at 25° C and, at Te, a tensile elongation of break of at least 8% and a tensile strength of at least 50 MPa. For the polymeric materials described herein, Te is selected such that Te-Tg > 20° C and Tm-Te is less than or equal to 150° C, 140° C, 130° C, or 120° C. Below the aforementioned tensile thresholds, the bead may be damaged when the mold sleeve is pulled over the bead during ejection, as explained in detail above. In some embodiments, the polymeric material has, at Te, a tensile elongation at break of no more than 15% or no more than 10% and a tensile strength at break of no more than 100 MPa or no more than 80 MPa. In some embodiments, the polymeric material has, at Te, a tensile elongation at break of from 8% to 15% or from 8% to 10% and a tensile strength at break of from 50 MPa to 100 MPa or from 50 MPa to 80 MPa. The person of ordinary skill in the art will recognize that each combination of ranges of tensile elongation at break and tensile strength at break is specifically contemplated and within the scope of the present disclosure. Tensile elongation at break and tensile strength at break can be measured according to ASTM D638 on molded tensile bars.

The Polymer

As noted above, the polymer is not particularly limited. In some embodiments, the concentration of the polymer in the polymeric material is greater than 30 wt. %, greater than 35 wt. % by weight, greater than 40 wt. % or greater than 45 wt. %. In some embodiments, the concentration of the polymer in the polymeric material is less than 99.95 wt.%, less than 99 wt.%, less than 95 wt.%, less than 90 wt.%, less than 80 wt. %, less than 70 wt. % or less than 60 wt. %. In some embodiments, the concentration of the polymer in the polymeric material is from 35 to 60 wt. % or from 40 to 55 wt. %. As used herein, wt.% is relative to the total weight of the polymeric material, unless explicitly noted otherwise. In some embodiments, the polymer is selected from the group of polymers consisting of polyamides, polysulfones, poly(aryl ether ketone)s (e.g. poly(ether ether ketone) and poly(arylene sulfide)s (e.g. polyphenylene sulfide).

In some embodiments, the polymer is a polyamide. As used herein, a polyamide refers to any polymer containing at least 50 mol% of recurring units including an amide bond (-NHOCO-). In some embodiments, the polyamide includes at least 50 mol% recurring units (RPA) formed from the polycondensation of a diamine and a dicarboxylic acid. Of course, in some embodiments, the polyamide includes at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or at least 99.5 mol% of recurring unit (RPA). AS used herein, mol% is relative to the total number of recurring units in the polyamide, unless explicitly noted otherwise. The diamine and dicarboxylic acid can be aliphatic or aromatic. As used herein, the term “aromatic” when referring to a diamine or dicarboxylic acid means that the diamine and dicarboxylic acid, respectively, includes one or more aromatic groups.

Examples of aliphatic diamines include, but are not limited to, Suitable aliphatic diamines are typically aliphatic alkylene diamines having 2 to 18 carbon atoms. Said aliphatic alkylene diamine is advantageously selected from the group consisting of 1,2-diaminoethane,

1.2-diaminopropane, propylene-1, 3-diamine, 1,3-diaminobutane, 1,4-diaminobutane,

1.5-diaminopentane, 1 ,4-diamino- 1 , 1 -dimethylbutane, 1 ,4-diamino- 1 -ethylbutane,

1 ,4-diamino- 1 ,2-dimethylbutane, 1 ,4-diamino- 1 ,3 -dimethylbutane, 1 ,4-diamino- 1 ,4- dimethylbutane, 1 ,4-diamino-2, 3 -dimethylbutane, 1 ,2-diamino- 1 -butylethane,

1.6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino-octane, l,6-diamino-2,5- dimethylhexane, l,6-diamino-2,4-dimethylhexane, l,6-diamino-3,3-dimethylhexane,

1.6-diamino-2,2-dimethylhexane, 1,9-diaminononane, 2-methylpentamethylenediamine,

1.6-diamino-2,2,4-trimethylhexane, l,6-diamino-2,4,4-trimethylhexane, l,7-diamino-2,3- dimethylheptane, l,7-diamino-2,4-dimethylheptane, l,7-diamino-2,5-dimethylheptane,

1.7-diamino-2,2-dimethylheptane, 1 , 10-decanediamine, 1 , 8-diamino- 1 ,3 -dimethyloctane,

1.8-diamino- 1,4-dimethyloctane, l,8-diamino-2,4-dimethyloctane, l,8-diamino-3,4- dimethyloctane, l,8-diamino-4,5-dimethyloctane, l,8-diamino-2,2-dimethyloctane,

1.8-diamino-3,3-dimethyloctane, l,8-diamino-4,4-dimethyloctane, l,6-diamino-2,4- diethylhexane, l,9-diamino-5-methylnonane, 1,11-diaminoundecane, 1,12-diaminododecane,

1.3-diaminocyclohexane, 1,4-diaminocyclohexane, l,3-bis(aminomethyl)cyclohexane,

1.4-bis(aminomethyl)cyclohexane, bis(3-methyl-4-aminocyclohexyl)-methane,

4,4'-methylene-bis-cyclohexylamine, isophoronediamine. Examples of aliphatic dicarboxylic acids include, but are not limited to, oxalic acid, malonic acid, succinic acid, glutaric acid, 2,2-dimethyl-glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecandioic acid, tetradecandioic acid, cis and/or trans cyclohexane- 1,4-dicarboxylic acid and cis and/or trans cyclohexane- 1 ,3 -dicarboxylic acid.

Examples of aromatic dicarboxylic acids include, but are not limited to, isophthalic acid, terephthalic acid, orthophthalic acid, and naphtalenedicarboxylic acids.

In some embodiments, the polyamide is an aliphatic polyamide. In such embodiments, recurring unit (R _PA ) is formed from the polycondensation of an aliphatic diamine and an aliphatic dicarboxylic acid. In some such embodiments, the aliphatic diamine is preferably selected from the group consisting of 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino- octane, 1,9-diaminononane, 2-methylpentamethylenediamine, 1,10-decanediamine,

1.11-diaminoundecane, 1,12-diaminododecane, 1,3-diaminocyclohexane,

1.4-diaminocyclohexane, l,3-bis(aminomethyl)cyclohexane,

1.4-bis(aminomethyl)cyclohexane, bis(3-methyl-4-aminocyclohexyl)-methane, and

4,4'-methylene-bis-cyclohexylamine. Additionally, the aliphatic dicarboxylic acid is selected from the group consisting of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecandioic acid, tetradecandioic acid, cis and/or trans cyclohexane-

1.4-dicarboxylic acid and cis and/or trans cyclohexane- 1, 3 -dicarboxylic acid. More preferably, the aliphatic diamine is selected from the group consisting of 1,6-diaminohexane and 1,10-decanediamine and the aliphatic dicarboxylic acid is selected from the group consisting of adipic acid, sebacic acid. Most preferably, the aliphatic polyamide includes recurring units (R _PA ) formed from the poly condensation of 1,6-diaminohexane and sebacic acid.

In some embodiments, the polyamide is a semi-aromatic polyamides. In some such embodiments, the recurring unit (R _PA ) is formed from the polycondensation of an aliphatic diamine with an aromatic dicarboxylic acid. In some such embodiments, the aliphatic diamine is preferably selected from the group consisting of 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diaminononane,

2-methylpentamethylenediamine, 1 , 10-decanediamine, 1,11 -diaminoundecane,

1.12-diaminododecane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, l,3-bis(aminomethyl)cyclohexane, l,4-bis(aminomethyl)cyclohexane, bis(3-methyl-4- aminocyclohexyl)-methane, and 4,4'-methylene-bis-cyclohexylamine. Additionally, the aromatic dicarboxylic acid is preferably selected from the group consisting of terephthalic acid and isophthalic acid. Most preferably, the semi-aromatic polyamide includes recurring unit (R _P A) formed from the poly condensation of 1,6-diaminohexane and terephthalic acid or 1,10-decanediamine and terephthalic acid.

In some embodiments, the polyamide is selected from the group consisting of PA 610, PA 6T, PA 9T, PA10T, PA 6T/66, PA 6T/9T, PA 6T/6I, PA6T/10T, PA 6T/6I/6, and PA 6T/6I/66.

The polyamide can be amorphous of semi-crystalline. As used herein, a semi crystalline polyamide has a heat of fusion (“D¾”) of at least 5 joules per gram (J/g) at a heating rate of 20° C/min. Similarly, as used herein, an amorphous polyamide has a D¾ of less than 5 J/g at a heating rate of 20C/min. D¾ can be measured according to ASTM D3418. Preferably, the polyamide is a semi-crystalline polyamide.

In some embodiments, the polyamide (PA) has a Tg of at least 50° C, at least 60° C, at least 100° C, at least 120° C, at least 130° C, or at least 140° C. Additionally or alternatively, in some embodiment, the polyamide (PA) has a Tg of no more than 190° C, no more than 180° C, no more than 170° C, or no more than 165° C. In some embodiments, the polyamide (PA) has a Tg of from 50° C to 190° C, from 60° C to 190° C, from 100° C to 190° C, from 110° C to 190° C, 120° C to 190° C, from 130° C to 180° C, from 130° C to 170° C, from 140° C to 170° C, from 145° C to 170° C, or from 145° C to 165° C. Preferably, for amorphous polyamides (PA), the Tg is from 130° C to 170° C and for semi-crystalline polyamides (PA) is from 60° C to 170° C. Tg can be measured according to ASTM D3418.

In some embodiments in which the polyamide (PA) is a semi-crystalline polyamide, the polyamide (PA) has a Tm of at least 170° C, at least 190° C, at least 200° C, at least 210° C, at least 220° C, at least 230° C, at least 240° C, or at least 250° C. Additionally or alternatively, in some embodiments in which the polyamide (PA) is a semi-crystalline polyamide, the polyamide (PA) has a Tm of no more than 400° C, no more than 390° C, no more than 380° C, no more than 370° C, no more than 360° C, or no more than 350° C. In some embodiments in which the polyamide (PA) is a semi-crystalline polyamide, the polyamide (PA) has a Tm of from 170° C to 400° C, from 190° C to 400° C, from 200° C to 400° C, from 210° C to 390° C, from 220° C to 380° C, from 230° C to 370° C, from 240° C to 360° C or from 250° C to 350° C. Tm can be measured according to ASTM D3418.

The polyamide (PA) described herein can be prepared by any polyamide synthesis methods known the person of ordinary skill in the art.

The Other Components As noted above, the polymeric material may also include a component selected from the group consisting of reinforcing agents, tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.

A large selection of reinforcing agents, also called reinforcing fibers or fillers, may be added to the composition according to the present invention. They can be selected from fibrous and particulate reinforcing agents. A fibrous reinforcing filler is considered herein to be a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a material has an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness of at least 5, at least 10, at least 20 or at least 50. In some embodiments, the reinforcing fibers (e.g. glass fibers or carbon fibers) have an average length of from 3 mm to 50 mm. In some such embodiments, the reinforcing fibers have an average length of from 3 mm to 10 mm, from 3 mm to 8 mm, from 3 mm to 6 mm, or from 3 mm to 5 mm. In alternative embodiments, the reinforcing fibers have an average length of from 10 mm to 50 mm, from 10 mm to 45 mm, from 10 mm to 35 mm, from 10 mm to 30 mm, from 10 mm to 25 mm or from 15 mm to 25 mm. The average length of the reinforcing fibers can be taken as the average length of the reinforcing fibers prior to incorporation into the polymeric material or can be taken as the average length of the reinforcing fiber in the polymeric material.

The reinforcing filler may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers and wollastonite. In embodiments in which the polymeric material includes a poly(arylene sulfide) (e.g. polyphenylene sulfide), the polymeric material preferably includes a reinforcing filler, preferably glass fiber or carbon fiber, most preferably glass fiber.

Among fibrous fillers, glass fibers are preferred; they include chopped strand A-, E-, C— , D-, S- and R-glass fibers, as described in chapter 5.2.3, p. 43 48 of Additives for Plastics Handbook, 2nd edition, John Murphy. Preferably, the filler is chosen from fibrous fillers. It is more preferably a reinforcing fiber that is able to withstand the high temperature applications.

The reinforcing agents may be present in the polymeric material in a total amount of greater than 15 wt. %, greater than 20 wt. % by weight, greater than 25 wt. % or greater than 30 wt. %. The reinforcing agents may be present in the polymeric material in a total amount of less than 65 wt. %, less than 60 wt. %, less than 55 wt. % or less than 50 wt. %.

The reinforcing filler may for example be present in the polymeric material in an amount ranging between 20 and 60 wt. %, for example between 30 and 50 wt. %.

The polymeric material of the present invention may also comprise a toughener. A toughener is generally a Tg polymer, with a Tg for example below room temperature, below 0°C or even below -25°C. As a result of its low Tg, the toughener are typically elastomeric at room temperature. Tougheners can be functionalized polymer backbones.

The polymer backbone of the toughener can be selected from elastomeric backbones comprising polyethylenes and copolymers thereof, e.g. ethylene-butene; ethylene-octene; polypropylenes and copolymers thereof; polybutenes; polyisoprenes; ethylene-propylene- rubbers (EPR); ethylene-propylene-diene monomer rubbers (EPDM); ethylene-acrylate rubbers; butadiene-acrylonitrile rubbers, ethylene-acrylic acid (EAA), ethylene-vinylacetate (EVA); acrylonitrile-butadiene-styrene rubbers (ABS), block copolymers styrene ethylene butadiene styrene (SEBS); block copolymers styrene butadiene styrene (SBS); core-shell elastomers of methacrylate-butadiene- styrene (MBS) type, or mixture of one or more of the above.

When the toughener is functionalized, the functionalization of the backbone can result from the copolymerization of monomers which include the functionalization or from the grafting of the polymer backbone with a further component.

Specific examples of functionalized tougheners are notably terpolymers of ethylene, acrylic ester and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylate; copolymers of ethylene, butyl ester acrylate and glycidyl methacrylate; ethylene-maleic anhydride copolymers; EPR grafted with maleic anhydride; styrene copolymers grafted with maleic anhydride; SEBS copolymers grafted with maleic anhydride; styrene-acrylonitrile copolymers grafted with maleic anhydride; ABS copolymers grafted with maleic anhydride.

The toughener may be present in the polymeric material in a total amount of greater than 1 wt. %, greater than 2 wt. % or greater than 3 wt. %. The toughener may be present in the polymeric material in a total amount of less than 30 wt. %, less than 20 wt. %, less than 15 wt. % or less than 10 wt. %.

The polymeric material may also comprise other conventional additives commonly used in the art, including plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.

The polymeric material may also comprise one or more other polymers, preferably polyamides different from the polyamide. Mention can be made notably of semi-crystalline or amorphous polyamides, such as aliphatic polyamides, semi-aromatic polyamides, and more generally the polyamides obtained by polycondensation between an aromatic or aliphatic saturated diacid and an aliphatic saturated or aromatic primary diamine, a lactam, an amino-acid or a mixture of these different monomers.

ARTICLES

The polymeric ports described herein can be desirably incorporated into articles designed fluid flow through a tube. In such embodiments, the tube is slid over the bead and the port conveys fluid from the tube into the body of the article or vice-versa. In some embodiments, the articles is an automotive component. Desirably, the automotive components are thermal management components including, but not limited to, thermostat housings, inlet/outlet ports, thermal modules, water pumps, and thermal valves. In some embodiments, the article can include a plurality of polymeric ports as described herein. For example, in some embodiments, the article can include at 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 polymeric ports. In such embodiments, the each polymeric port can be distinct, some polymeric ports can be distinct, or no polymeric ports can be distinct.

The embodiments above are intended to be illustrative and not limiting. Additional embodiments are within the inventive concepts. In addition, although the present invention is described with reference to particular embodiments, those skilled in the art will recognized that changes can be made in form and detail without departing from the spirit and scope of the invention. Any incorporation by reference of documents above is limited such that no subject matter is incorporated that is contrary to the explicit disclosure herein.