Foamable compositions and methods for making foamed articles
阅读说明：本技术 用于制造泡沫制品的可发泡的组合物和方法 (Foamable compositions and methods for making foamed articles ) 是由 C·A·格鲁 N·M·罗莎 C·M·格鲁 于 2018-12-03 设计创作，主要内容包括：在一个方面中,公开了可发泡的组合物,其包括原料聚合物、与原料聚合物共混的滑石和柠檬酸盐(酯)化合物。在一些实施方式中,组合物中滑石的浓度在按重量计约0.05％至约25％的范围内,例如,在约2％至约20％的范围内、或在约3％至约15％的范围内或在约5％至约10％的范围内。此外,组合物中柠檬酸盐(酯)化合物的浓度可以,例如,在按重量计约0.05％至约3％的范围内、或在按重量计约0.02％至约0.9％的范围内、或在按重量计约0.03％至约0.8％的范围内、或在按重量计约0.04％至约0.7％的范围内或在按重量计约0.05％至约0.6％的范围内。(In one aspect, a foamable composition is disclosed that includes a base polymer, talc blended with the base polymer, and a citrate compound. In some embodiments, the concentration of talc in the composition is in the range of about 0.05% to about 25% by weight, for example, in the range of about 2% to about 20%, or in the range of about 3% to about 15% or in the range of about 5% to about 10%. Further, the concentration of the citrate compound in the composition may, for example, be in the range of about 0.05% to about 3% by weight, or in the range of about 0.02% to about 0.9% by weight, or in the range of about 0.03% to about 0.8% by weight, or in the range of about 0.04% to about 0.7% by weight or in the range of about 0.05% to about 0.6% by weight.)
1. A composition, comprising:
the starting polymer is a polymer of a polymer,
talc blended with said base polymer, and
a citrate compound blended with the base polymer.
2. The composition of claim 1, wherein the concentration of the talc in the composition is in the range of about 0.3% to about 30% by weight.
3. The composition of claim 2, wherein the concentration of the talc in the composition is in the range of about 2% to about 20% by weight.
4. The composition of claim 2, wherein the concentration of the talc in the composition is in the range of about 3% to about 15%.
5. The composition of claim 2, wherein the concentration of the talc in the composition is in the range of about 5% to about 10%.
6. The composition of claim 1, wherein the concentration of the citrate compound in the composition is in the range of about 0.01% to about 1% by weight.
7. The composition of claim 6, wherein the concentration of the citrate compound in the composition is in the range of about 0.02% to about 0.9% by weight.
8. The composition of claim 6, wherein the concentration of the citrate compound in the composition is in the range of about 0.03% to about 0.8% by weight.
9. The composition of claim 6, wherein the concentration of the citrate compound in the composition is in the range of about 0.04% to about 0.7% by weight.
10. The composition of claim 6, wherein the concentration of the citrate compound in the composition is in the range of about 0.05% to about 0.6% by weight.
11. The composition of claim 1, wherein the concentration of the base polymer ranges from about 50% to about 98.5% by weight.
12. The composition of claim 1, wherein the base polymer comprises a fluoropolymer.
13. The composition of claim 1, wherein the base polymer comprises a perfluoropolymer.
14. The composition of claim 11, wherein the fluoropolymer comprises any of tetrafluoroethylene/perfluoromethyl vinyl ether copolymer (MFA), hexafluoropropylene/tetrafluoroethylene copolymer (FEP), Perfluoroalkoxy (PFA), and perfluoroalkoxyalkane, and combinations thereof.
15. The composition of claim 1, wherein the polymer comprises any of polyphenylene sulfide (PPS), Polyetherimide (PSU), polyphenylsulfone (PPSU), polyethersulfone (PES/PESU), Polyetheretherketone (PEEK), Polyaryletherketone (PAEK), Polyetherketoneketone (PEKK), Polyetherketone (PEK), Cyclic Olefin Copolymer (COC), Polycarbonate (PC), polyphenylene ether (PPE), Liquid Crystal Polymer (LCP), and/or combinations thereof.
16. The composition of claim 1, wherein the citrate compound comprises any one of calcium citrate, potassium citrate, zinc citrate, and combinations thereof.
17. The composition of claim 1, wherein the composition is in the form of a plurality of pellets.
18. The composition of claim 1, further comprising a nucleating agent blended with the base polymer.
19. The composition of claim 18, wherein the nucleating agent comprises any of PTFE (polytetrafluoroethylene), boron nitride, zinc borate, zinc oxide, or titanium dioxide.
20. The composition of claim 18, wherein the concentration of the nucleating agent ranges from about 0.1% to about 3% by weight.
21. The composition of claim 18, further comprising an Aclyn wax blended with the base polymer.
22. The composition of claim 21, wherein the concentration of the Aclyn wax is in the range of about 0.1% to about 0.75%.
23. The composition of claim 1, wherein the composition is capable of pipe extrusion, semi-pressure extrusion, or pressure extrusion at an extrusion pressure of any of less than 3500psi or 2500 psi.
24. A method for making a foam article comprising: heating a composition comprising a base polymer, talc blended with the base polymer, and a citrate compound blended with the base polymer to a temperature sufficient to cause decomposition of the talc, so as to generate a gas for foaming the composition.
25. The method of claim 24, further comprising extruding the heated composition to form the foam article.
26. The method of claim 24, wherein the foam article is a separator suitable for use in a communication cable.
27. The method of claim 24, wherein the temperature is at least about 600F.
28. The method of claim 24, wherein the citrate compound comprises any one of calcium citrate, potassium citrate, and zinc citrate.
29. The method of claim 24, wherein the concentration of the talc in the composition is in the range of about 0.3% to about 30% by weight.
30. The method of claim 29, wherein the concentration of the talc in the composition is in the range of about 2% to about 20% by weight.
31. The method of claim 29, wherein the concentration of the talc in the composition is in the range of about 3% to about 15%.
32. The method of claim 29, wherein the concentration of the talc in the composition is in the range of about 5% to about 10%.
33. The method of claim 24, wherein the concentration of the citrate compound in the composition is in the range of about 0.01% to about 1% by weight.
34. The method of claim 33, wherein the concentration of the citrate compound in the composition is in the range of about 0.02% to about 0.9% by weight.
35. The method of claim 33, wherein the concentration of the citrate compound in the composition is in the range of about 0.03% to about 0.8% by weight.
36. The method of claim 33, wherein the concentration of the citrate compound in the composition is in the range of about 0.04% to about 0.7% by weight.
37. The method of claim 33, wherein the concentration of the citrate compound in the composition is in the range of about 0.05% to about 0.6% by weight.
38. The method of claim 24, wherein the concentration of the base polymer ranges from about 50% to about 95% by weight.
39. The method of claim 24 wherein the base polymer comprises a fluoropolymer.
40. The method of claim 24, wherein the base polymer comprises a perfluoropolymer.
41. The method of claim 39, wherein the fluoropolymer comprises any of tetrafluoroethylene/perfluoromethyl vinyl ether copolymer (MFA), hexafluoropropylene/tetrafluoroethylene copolymer (FEP), Perfluoroalkoxy (PFA), and perfluoroalkoxyalkane, and combinations thereof.
42. The method of claim 24, wherein the polymer comprises any one of polyphenylene sulfide (PPS), Polyetherimide (PSU), polyphenylsulfone (PPSU), polyethersulfone (PES/PESU), Polyetheretherketone (PEEK), Polyaryletherketone (PAEK), Polyetherketoneketone (PEKK), Polyetherketone (PEK), Cyclic Olefin Copolymer (COC), Polycarbonate (PC), polyphenylene ether (PPE), Liquid Crystal Polymer (LCP), and/or combinations thereof.
43. The method of claim 24, wherein the composition is in the form of a plurality of pellets.
44. The method of claim 25 wherein the heated composition is extruded on any of 16AWg or 18AWg copper wire to form a foam insulator.
45. The method of claim 25, wherein the step of extruding the heated composition comprises pressure extruding the heated composition.
46. The method of claim 45, wherein the step of pressure extruding comprises maintaining a pressure experienced by the heated composition of less than about 3500 psi.
47. The method of claim 46, wherein the step of pressure extruding comprises maintaining a pressure to which the heated composition is subjected of less than about 2500 psi.
48. A cable, comprising:
a partition providing a plurality of channels for receiving one or more transmission media, the partition comprising a plurality of porous structures distributed therein at a foam rate of at least about 40%,
at least one electrical conductor disposed in one of the channels, the electrical conductor configured for transmission of both communication data and electrical power, an
An outer jacket surrounding the separator and the at least one electrical conductor.
49. The cable of claim 48, wherein the separator exhibits a foaming ratio of at least about 50%.
50. The cable of claim 49, wherein the separator exhibits a foaming ratio in the range of about 50% to about 70%.
51. The cable of claim 48 wherein the wire comprises a foamed electrical insulation having a foaming ratio of at least about 35%.
52. The cable of claim 51, wherein the foam fraction of the electrical insulation is in the range of about 35% to about 60%.
53. The cable of claim 48 wherein the outer jacket comprises a plurality of cellular structures distributed therein at a foam rate of at least about 30%.
54. The cable of claim 53 wherein the jacket exhibits a foam fraction in the range of about 30% to about 50%.
55. The cable of claim 48, further comprising at least one optical fiber placed in one of the other channels.
56. The cable according to claim 55, wherein the optical fiber comprises a foam buffer.
57. The cable of claim 56, wherein the foam cushion exhibits a foam rate in a range of about 30% to about 50%.
Drawings
Figure 1 schematically depicts a plurality of pellets according to an embodiment of the invention,
figure 2 is a flow chart depicting various steps in a method for producing a foamed article according to the present invention,
figure 3 is a schematic front view of a foamed article, separator according to an embodiment of the invention,
figure 4 schematically illustrates a foam cable jacket according to an embodiment of the present invention,
figure 5 schematically illustrates an insulated conductor having a foamed insulation according to an embodiment of the present invention,
FIG. 6 schematically depicts a plurality of pellets according to an embodiment of the invention, wherein each pellet comprises a base polymer, talc and a citrate compound blended in the base polymer,
figure 7 schematically depicts an extrusion apparatus suitable for use in the practice of some embodiments of making foam articles using polymers according to the present teachings,
FIG. 8 schematically depicts a pressure extrusion apparatus suitable for use in the practice of some embodiments of making a foam article using a polymer according to the present teachings, and
FIG. 9 schematically depicts a cable that may be used for transmission of electrical power and communication data according to an embodiment of the present teachings.
Detailed Description
The present invention generally provides foamable polymeric compositions that can be used to form a wide variety of articles, such as components of communication cables. In particular, it has been found that the use of talc in a polymeric composition with a citrate compound, such as citrate, can advantageously provide increased foaming of the polymeric composition for the manufacture of a wide variety of foamed articles. In other words, it has been found that talc and citrate compounds act synergistically to provide increased foam. In some embodiments, the composition according to the invention is in the form of a plurality of pellets.
Various terms are used herein according to their ordinary meaning. For greater clarity, the following terms are further defined below.
The term "talc" as used herein generally refers to a natural or synthetic hydrous magnesium silicate compound. In some embodiments, the talc mineral comprises a mineral having the formula: 3MgOSiO2H2Magnesium silicate hydride represented by O, wherein SiO is used in some cases2About 64.5 weight percent, MgO about 31.9 weight percent and H2O is about 4.75 weight percent. In some cases, talc may include other minerals such as magnesite, chlorite, magnetite, carbonate, and dolomite.
The term "engineering resin" or "engineering polymer" as used herein refers to any of the following polymers: polyphenylene Sulfide (PPS), Polyetherimide (PEI), Polysulfone (PSU), polyphenylsulfone (PPSU), polyethersulfone (PES/PESU), Polyetheretherketone (PEEK), Polyaryletherketone (PAEK), Polyetherketoneketone (PEKK), Polyetherketone (PEK), or polyolefins such as Polyethylene (PE), polypropylene (PP), Cyclic Olefin Copolymer (COC), Polycarbonate (PC), polyphenylene ether (PPE), Liquid Crystal Polymer (LCP), and/or combinations thereof.
The term "about" as used herein is intended to indicate up to 10% of the variable.
The term "foamed article" as used herein refers to the manufacture of an article comprising a plurality of cellular structures.
The terms "foam rate" or "foaming rate" are used interchangeably herein to refer to the ratio of the volume of pores in a porous structure, e.g., a porous separator, to the total volume of the structure.
Referring to fig. 1, in some embodiments, the present invention provides a plurality of
A wide variety of polymers may be used as the base polymer. Some examples of suitable polymers include, but are not limited to, fluoropolymers such as perfluoropolymers, engineering resins, and the like. Some specific examples of suitable polymers include, but are not limited to, tetrafluoroethylene/perfluoromethyl vinyl ether copolymer (MFA), hexafluoropropylene/tetrafluoroethylene copolymer (FEP), Perfluoroalkoxy (PFA), and perfluoroalkoxyalkanes, and combinations thereof. Some other examples of suitable polymers include, but are not limited to, polyphenylene sulfide (PPS), Polyetherimide (PSU), polyphenylsulfone (PPSU), polyethersulfone (PES/PESU), Polyetheretherketone (PEEK), Polyaryletherketone (PAEK), Polyetherketoneketone (PEKK), Polyetherketone (PEK), and combinations thereof.
In some embodiments, the citrate compound may be a citrate salt. Some suitable examples of citrate salts include, but are not limited to, calcium citrate, potassium citrate, zinc citrate, and combinations thereof.
The combination of talc and citrate compound advantageously allows for increased foaming of the
In some embodiments, the foaming of the composition according to the present teachings can result in a foamed article, such as a separator suitable for use in a communication cable, comprising a plurality of porous structures distributed therein. In some embodiments, at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90% or all of the porous structure may be in the form of closed pores. Further, in some embodiments, such porous structures may have a maximum dimension in the range of about (0.5 mils to 5 mils, i.e., 0.0005 inches to 0.005 inches).
Referring to the flow diagram of fig. 2, in a related aspect, a method for manufacturing a foamed article is disclosed, including heating a composition including a base polymer, talc blended with the base polymer, and a citrate compound blended with the base polymer to a temperature sufficient to cause decomposition of at least the talc so as to generate a gas for the foamed composition. For example, the composition may be heated to a temperature of at least about 600 ° F, or at least about 610 ° F, or at least about 620 ° F, or at least about 630 ° F, or at least about 640 ° F. In some embodiments, the heated composition can be extruded to form a foamed article, such as a foamed separator, for a communication cable. In some such embodiments, pressure extrusion is applied to manufacture the foam article, as discussed in greater detail first below.
In some embodiments of the above method, the citrate compound can be, for example, citrate. Some examples of citrate salts suitable for use in the above methods include, but are not limited to, calcium citrate, potassium citrate, zinc citrate, and combinations thereof. The concentration of any of the talc and citrate compounds can be any of those discussed above. In addition, a wide variety of polymers, such as those discussed above, may be used in the above compositions, which are heated to form the foamed article as discussed above.
Fig. 3 schematically depicts a foamed article 20 in the form of a separator suitable for use in a communication cable, formed using a method according to the present invention. The divider 20 includes a central portion 22 with a plurality of arms 24 extending from the central portion 22 that provide a plurality of channels 28, and a variety of mediums, such as insulated twisted copper pairs, may be placed in the plurality of channels 28. The separator 20 may be in the form of a polymer, such as those discussed above, in which a plurality of porous structures are distributed. In this embodiment, the porous structure is in the form of a gas-filled cavity. In some embodiments, the maximum dimension of these porous structures, for example, the diameter of the porous structures when they have a spherical shape, may be, for example, in the range of about (0.5 to 5 mils, i.e., 0.0005 to 0.005 inches).
In some embodiments, the volume of the porous structure is at least about 40%, or at least about 50%, or at least about 60%, or at least about 70% of the volume of the separator. Further, in some embodiments, at least about 40%, or at least about 50%, or at least about 60%, or at least about 70% of the porous structure may be in the form of closed porosity.
Fig. 4 schematically depicts a
Fig. 5 schematically depicts an insulated conductor 50, e.g., an insulated copper wire, having a center conductor 52 covered by an insulator 54. In this embodiment, an insulator is formed in accordance with the present teachings and includes a plurality of porous structures 56. More specifically, in this embodiment, the insulator 54 may be in the form of a polymer, such as those discussed above, in which a plurality of porous structures 56 are distributed. In this embodiment, the porous structure is in the form of a gas-filled cavity. In some embodiments, the maximum dimension of these porous structures, for example, the diameter of the porous structures when they have a spherical shape, may be, for example, in the range of about (0.5 to 5 mils, i.e., 0.0005 to 0.005 inches). In some embodiments, the insulator 54 may exhibit a foaming ratio of at least about 35%, for example, in the range of about 35% to about 60%.
As noted above, in some embodiments, compositions according to the present teachings can include a base polymer, talc, a citrate compound, and a nucleating agent such as PTFE. For example, FIG. 6 schematically depicts a plurality of pellets 600, each of which comprises a base polymer 601, talc 602, a citrate compound 603, and, for example, PTFE or TiO2To (1)A nucleating agent 604, which is distributed throughout the base polymer. In some such embodiments, the concentration of the base polymer may, for example, be in the range of about 75% to about 99% by weight, the concentration of talc may be in the range of about 0.05% to about 30% by weight, the concentration of citrate compound may be in the range of about 0.05% to about 3% by weight, and the concentration of nucleating agent may be in the range of about 0.1% to about 3% by weight. Further, in some such embodiments, the Aclyn wax may be added to the composition, for example, at a weight concentration in the range of about 0.05% to about 2%.
As noted above, in some embodiments, foamable compositions according to the present teachings can be heated and extruded to produce a wide variety of foam articles, such as insulation and wire insulation.
For example, fig. 7 schematically depicts a cross-head 700 of an extrusion device that may be used to extrude molten polymer. Polymer 702 flows into cross-head 700 through an extruder (not shown). Clamping surface 704 connects the crosshead to the extruder. The clamping surface 704 is typically heated to a temperature in the range of about 720 ° F to about 750 ° F. The valve portion 705 of the crosshead is heated to a temperature in the range of about 730 deg.f to about 760 deg.f. Crosshead 700 includes a die 706 and an extrusion tip 708 that indicates the thickness of polymer covering a defined gauge size. The mold is typically heated to an elevated temperature in the range of about 730 ° F to about 780 ° F. More specifically, in this embodiment, wire 710 enters the crosshead through its back and passes through the inside of the crosshead until it meets the polymer. Rotating screw 712 advances the polymer through the crosshead to the exit of the die. The extrusion tip 708 extends to the exit of the die 706. In particular, the tip 708 has a land area (land)708a in the form of a metal cylindrical portion that extends the extrusion tip to the exit of the die. As a result, the molten polymer coats the wires outside the mold. Therefore, the process pressure is significantly reduced due to the coating of the wire with the molten polymer.
In some embodiments, a plurality of different types of foam articles may be manufactured by pressure extruding a composition according to the present teachings. By way of example, fig. 8 schematically depicts a
In a related aspect, a pressure extrusion apparatus as discussed above may be applied to form a wide variety of foamed articles, for example, using fluoropolymers and/or engineering resins as base polymers, in which one or more chemical blowing agents are blended. Although in some embodiments the chemical foaming agent may be talc, in other embodiments other chemical foaming agents may be used. Some examples of such other chemical blowing agents include, but are not limited to, magnesium carbonate, calcium carbonate, and magnesium hydroxide. In many such applications, the pressure is maintained in the range of about 2500psi to about 4500psi during extrusion.
Figure 9 schematically depicts a cable 900 according to an embodiment of the present teachings that includes a cross-shaped divider 901 configured to provide a plurality of channels 902 for receiving a transmission medium. Wires (e.g., copper wires) 904a, 904b, and 904c are placed in three channels 902 of the partition and optical fibers 905 are placed in the remaining channels of the partition. In this embodiment, at least one of the wires, e.g., wire 904a, is capable of transmitting not only communication data, but also power. For example, the wire 904a may have an AWG in the range of about 8 to about 28, such as an AWG in the range of 16 to 22 (e.g., 18). In some such embodiments, the wire 904a is capable of carrying a current in a range of about 0.5 amps to about 1amp and up to about 200 watts of electrical power, for example, in a range of about 10 watts to about 200 watts of electrical power.
An outer jacket 906 surrounds the separator and the transmission medium. In this embodiment, the separator 900 is formed as a foamed polymeric article, for example, using one or more polymers disclosed herein, in which a plurality of porous structures 900a are distributed. In some such embodiments, the partition exhibits a foaming ratio of at least about 40%, for example, in the range of about 50% to about 70%, for example, in the range of about 60% to about 70%. Each of the wires 904a, 904b, and 904c includes a center conductor 904a ', 904b ', 904c ' surrounded by an insulation layer 904a ", 904 b", and 904c ". In some embodiments, one or more of insulating layers 904a ", 904 b", and 904c "are formed as a foamed polymer, such as a polymer disclosed herein. In some such embodiments, the foamed insulation layer may exhibit a foaming ratio of at least about 35%, for example, a foaming ratio in the range of about 35% to about 60%. Further, in some embodiments, outer jacket 906 may also be formed as a foamed polymeric article, for example, using one or more polymers disclosed herein. In some such embodiments, the outer cover 906 may exhibit a foaming ratio of at least about 30%, for example, in the range of about 30% to about 50%. In this embodiment, the optical fiber 905 comprises a foam buffer 905', in which a plurality of porous structures 905 "are distributed. In some embodiments, the foam cushion 905' exhibits a foaming rate in the range of about 30% to about 50%, for example, a foaming rate in the range of about 35% to about 40%. In some embodiments, the buffer of the optical fiber is formed by using a blend of PEEK (polyetheretherketone) and FEP (e.g., 50/50 blend by weight).
Cable 900 may be used as a data/communication cable to simultaneously power and communicate with a device. Non-limiting examples of such applications include security cameras, computers, wireless access points, antenna systems or Distributed Antenna Systems (DAS), LED lighting, factory/office automation systems, robotics applications, unmanned cars/trucks, HVAC (heating/air conditioning) systems, video surveillance cameras, and the like.
The following examples are provided for illustrative purposes and do not necessarily indicate the best mode for carrying out the invention.
Example 1
A blend of FEP polymer with talc and calcium citrate is formed. The concentration of FEP polymer in the blend was about 94% by weight, while the concentrations of talc and calcium citrate in the blend were 3.75% and 0.05% by weight, respectively. The blend also included Aclyn wax (0.05% by weight). It is to be understood that the use of Aclyn wax is optional and may not be employed in other instances. The blend is compounded to produce a plurality of pellets.
Another blend of FEP polymer with talc and without calcium citrate is also formed. The concentration of FEP polymer in the blend is about 94% by weight and the concentration of calcium citrate is about 0.05% by weight. The blend also included Aclyn wax (0.05% by weight).
Pellets comprising FEP, talc and citrate (citrate), as well as pellets comprising FEP and talc without citrate, were treated separately using the process parameters indicated in table 1 below. Pellets were processed on a 1.5 inch high temperature extruder using a 26: 1L/D of a general screw. The ingredients that make up the blend are mixed together on a production line and then placed directly into the hopper of an extruder.
TABLE 1
The above results show that the use of talc together with citrate results in a much improved foaming rate relative to the use of talc alone. In particular, 59% foaming was observed for pellets containing both talc and citrate, while 32% foaming was observed for pellets containing only talc.
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