Patent Application
20180346676
This invention relates to polyethylene (PE) foams. In one aspect, the invention relates to PE foams useful as telecom insulation while in another aspect, the invention relates to coaxial and radio frequency cables comprising PE foams.
Coaxial/radio frequency cables made of highly foamed polyethylene are widely used as antenna feeders, cabling of antenna arrays, equipment interconnections, mobile telecommunication systems, microwave transmission systems, broadcast transmission systems and other communication systems. As demand for high bandwidth increases, cables require the use of a highly foamed dielectric made with polymer resins, e.g., a polyolefin, with minimum polar groups or polar additives and which are cost effective and have good electrical properties.
Usually, a high frequency cable is made of an inner conductor surrounded by a foamed insulation. The base resin for insulation is generally a mixture of high density polyethylene (HDPE), high pressure low density polyethylene (HPLDPE, or simply, LDPE) and a nucleating master batch. In general, the ratio of HDPE to LDPE is 70-80% HDPE/30-20% LDPE. The nucleating master batch is typically added at about 1-3% and is generally also based on a LDPE resin. Due to less branching in the molecular structure of HDPE, the dissipation factor (Df) of HDPE is lower than LDPE and as such, the majority of base resin for cable insulation is typically HDPE. Moreover, this provides desirable mechanical properties to the foam such as high crush resistance. LDPE, in contrast, enhances the overall melt strength of the base resin due to its branched structure.
In early attempts, the foaming step was implemented by compounding the base polymer resin with a specific chemical foaming agent capable of blowing closed cells of desired size. For a typical wire and cable gas injection foaming line, the porosity of the HDPE/LDPE (7/3) blend can reach 75-80% depending on customer lines. However, chemical foaming processes can only achieve lower levels of foaming and also suffer from the fact that the polymeric dielectric material traps residue of the foaming agent that deteriorates the dissipation factor. The lower foaming level and presence of residues from the foaming agent result in higher signal attenuation, especially at the upper end of the frequency range.
Physical foaming of polymers is generally carried out by dissolving a blowing agent into the polymer matrix. Subsequently, the solubility of the blowing agent is reduced rapidly by producing thermodynamic instability in the structure (e.g., by increasing temperature or decreasing pressure), to induce nucleation and the growth of bubbles. The industrial practice for physical foaming for cable insulations is based on the similar concept by injecting an inert gas (such as nitrogen) to blow the gas filled expanded cell. Adding a nucleating agent is a frequently used and effective technique to reduce cell size, enhance cell density and uniform cell distribution.
For the current nitrogen (N2) foaming process, the resulting porosity is in the range of 50-80%, and, correspondingly, the Df of current PE foam is around 0.0002-0.00015 (at 2.47 Ghz), which marginally meets the current high-end cable requirement. However, the insulation need for reduced cable attenuation with higher frequency remains unmet. Increasing the expansion ratio of the insulation of telecom cable is one way to reduce Df. The expansion ratio is a measure of the void, or empty space, in the insulation and is generally measured as the ratio of the volume of the voids to the total volume of the foam. Attempts at higher porosity in the N2 foaming process often result in foam cell collapse and non-uniform structures. Either a new PE base formulation or a breakthrough in foaming process is required to enable the production of high porosity PE insulation foam in cable industry.
In one embodiment the invention is a process for making a foam composition, the process comprising the steps of:
In one embodiment, the invention is a foam composition made by the process described above.
The foams of this invention exhibit a high expansion ratio of up to 85% porosity. The peroxide is used in relatively small amounts and in one embodiment, the foaming step is performed with supercritical carbon dioxide (ScCO2). In one embodiment, the peroxide modified polymer blend has a low Df value of 15*10−5.
In one embodiment, the process of the invention produces a foam composition useful in the manufacture of cables for use in high frequency applications (greater than (>) 3 GHz). The foams made by the process of the invention (1) comprise an HDPE/LDPE blend with a low Df value, e.g., about 11*10−5, and (2) exhibit a slight crosslinking via reaction with peroxide, e.g., DTAP. The former favors a foam with a low Df value and the latter favors good melt strength for the resins but a minimum negative impact on dissipation factor, (mixture of (A)) which, in turn, further improves the porosity of the foam. In this invention, the ScCO2 foaming process is applied and pure CO2 is used as blowing agent during present foaming process.
Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight and all test methods are current as of the filing date of this disclosure. For purposes of United States patent practice, the contents of any referenced patent, patent application or publication are incorporated by reference in their entirety (or its equivalent US version is so incorporated by reference), especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.
The numerical ranges disclosed herein include all values from, and including, the lower and upper value. For ranges containing explicit values (e.g., 1 or 2; or 3 to 5; or 6; or 7), any subrange between any two explicit values is included (e.g., 1 to 2; 2 to 6; 2.5 to 6.5; 5 to 7; 3 to 7; 5 to 6; etc.).
“High pressure CO2” and like terms means CO2 at a pressure of greater than ambient pressure (>0.1 MPa), including CO2 in a sub-critical or super-critical state. The critical pressure of CO2 is 7.4 MPa.
A “high density polyethylene” (or “HDPE”) is an ethylene-based polymer having a density of at least 0.94 g/cc, or from at least 0.94 g/cc to 0.98 g/cc. The HDPE has a melt index from 0.1 g/10 min to 25 g/10 min.
The HDPE can include ethylene and one or more C3-C20 α-olefin comonomers. The comonomer(s) can be linear or branched. Nonlimiting examples of suitable comonomers include propylene, 1-butene, 1 pentene, 4-methyl- 1-pentene, 1-hexene, and 1-octene. The HDPE can be prepared with either Ziegler-Natta, chromium-based, constrained geometry or metallocene catalysts in slurry reactors, gas phase reactors or solution reactors. The ethylene/C3-C20 α-olefin comonomer includes at least 50 percent by weight ethylene polymerized therein, or at least 70 percent by weight, or at least 80 percent by weight, or at least 85 percent by weight, or at least 90 weight percent, or at least 95 percent by weight ethylene in polymerized form.
In an embodiment, the HDPE is an ethylene/a-olefin copolymer with a density from 0.95 g/cc to 0.98 g/cc, and a melt index from 0.1 g/10 min to 10 g/10 min. In an embodiment, the HDPE has a density from 0.960 g/cc to 0.980 g/cc, and a melt index from 0.1 g/10 min to 10 g/10 min.
In an embodiment, the HDPE has a density from 0.95 g/cc, or 0.96 g/cc to 0.97 g/cc and a melt index from 0.1 g/10 min to 10 g/min.
In an embodiment, the HDPE has a density from 0.96 g/cc to 0.98 g/cc and a melt index from 1.0 g/10 min to 10.0 g/10 min.
Nonlimiting examples of suitable HDPE include ELITE 5960G, HDPE KT 10000 UE, HDPE KS 10100 UE and HDPE 35057E, each available from The Dow Chemical Company Midland, Mich., USA; and SURPASS® available from Nova Chemicals Corporation, Calgary, Alberta, Canada.
The LDPE resins are well known in the art, commercially available, and made by any one of a wide variety of processes including, but not limited to, solution, gas or slurry phase, and high pressure tube or autoclave; Ziegler-Natta, metallocene or constrained geometry catalyzed (CGC); etc. These resins have a density of 0.915 to 0.925 g/cm3, and a melt index (MI, I2) of 0.15 to 50 grams per 10 minutes (g/10 min). The polyethylene can have a broad molecular weight distribution, characterized by a polydispersity (Mw/Mn) of greater than 3.5, or a narrow molecular weight distribution, characterized by a polydispersity (Mw/Mn) in the range of 1.5 to 3. Mw is defined as weight average molecular weight, and Mn is defined as number average molecular weight.
Commercially available LDPE resins include but are not limited to DOW Low Density Polyethylene resins available from The Dow Chemical Company and, in general, any fractional melt flow index (MFI) resin for use in heavy duty bags or agricultural films such as those available from Borealis, Basel, Sabic and others.
Specific examples of LDPE useful in this invention include homogeneously branched, linear ethylene/alpha-olefin copolymers (e.g. TAFMER™ by Mitsui Petrochemicals Company Limited and EXACT™ by Exxon Chemical Company), homogeneously branched, substantially linear ethylene/alpha-olefin polymers (e.g., AFFINITY™ and ENGAGE™ polyethylene available from The Dow Chemical Company), and olefin block copolymers such as those described in U.S. Pat. No. 7,355,089 (e.g., INFUSE™ available from The Dow Chemical Company). The more preferred LDPE are the homogeneously branched linear and substantially linear ethylene copolymers. The substantially linear ethylene copolymers are especially preferred, and are more fully described in U.S. Pat. Nos. 5,272,236, 5,278,272 and 5,986,028. HDPE/LDPE Blend
The amount of HDPE in the HDPE/LDPE blend, based on the weight of the composition, is typically at least 45 weight percent (wt %), more typically at least 55 wt % and even more typically at least 60 wt %. The amount of HDPE in the polyolefin composition, based on the weight of the composition, typically does not exceed 95 wt %, more typically it does not exceed 85 wt % and even more typically it does not exceed 80 wt %. The amount of LDPE in the HDPE/LDPE blend, based on the weight of the composition, is typically at least 5 weight percent (wt %), more typically at least 15 wt % and even more typically at least 20 wt %. The amount of LDPE in the polyolefin composition, based on the weight of the composition, typically does not exceed 55 wt %, more typically it does not exceed 45 wt % and even more typically it does not exceed 40 wt %. In one embodiment, a minor amount, e.g., less than 5, or 4, or 3, or 2, or 1, wt % of one or more other polymers, e.g., one or more other polyolefins such as polypropylene, may be present in the blend.
Suitable free radical initiators used as crosslinking agents are the dialkyl peroxides and diperoxyketal initiators. These compounds are described in the Encyclopedia of Chemical Technology, 3rd edition, Vol. 17, pp. 27-90 (1982). Mixtures of two or more free radical initiators may also be used together as the free radical initiator.
In the group of dialkyl peroxides, nonlimiting examples of suitable free radical initiators are: dicumyl peroxide; di-t-butyl peroxide; t-butyl cumyl peroxide; 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane; 2,5-dimethyl-2,5 -di(t-amylperoxy)-hexane; 2,5 -dimethyl-2,5 -di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5 -di(t-amylpero-xy)hexyne-3; α,α-di[(t-butylperoxy)-isopropyl]-benzene; di-t-amyl peroxide (DTAP); 1,3,5-tri-[(t-butylperoxy)-isopropyl]benzene; 1,3 -dimethyl-3 -(t-butylperoxy)butanol; 1,3 -dimethyl-3 -(t-amylperoxy) butanol; and mixtures of two or more of these initiators.
In the group of diperoxyketal initiators, nonlimiting examples of suitable free radical initiators include: 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(t-butylperoxy)-cyclohexane n-butyl; 4,4-di(t-amylperoxy)valerate; ethyl 3,3-di(t-butylperoxy)butyrate; 2,2-di(t-amylperoxy)propane; 3,6,6,9,9-pentamethyl-3 -ethoxycarbonylmethyl-1,2,4,5-tetra-oxacyclononane; n-butyl-4,4-bis(t-butylperoxy)-valerate; ethyl-3,3 -di(t-amylperoxy)-butyrate; and mixtures of two or more of these initiators.
The amount of free radical initiator present in the composition can vary with the minimum amount being sufficient to afford the desired range of crosslinking. The minimum amount of peroxide is at least about 0.02 wt %, or at least about 0.05 wt %, or at least about 0.1, weight percent (wt %) based upon the weight of the HDPE/LDPE blend. The maximum amount of free radical initiator in the composition can vary, and it is typically determined by such factors as cost, efficiency and degree of desired crosslinking. The maximum amount may be less than about 2 wt %, or less than about 1 wt %, or less than about 0.5, wt % based upon the weight of the HDPE/LDPE blend.
“Polydimethylsiloxane fluids”, “ polymeric organosilicon materials” and like terms refer to a variety of siloxane-based polymers having repeating units based on Formula (I), such as, for example, XIAMETER™ PMX-200 Silicone Fluid 1,000 CS from Dow Corning Corporation having a kinetic viscosity of 1000 centistokes.
Nucleating agents, such as fluororesin particles (e.g., polytetrafluoroethylene (PTFE)), azodicarbonamide (ADCA), talc, silica, zeolites, boron nitride and the like, including mixtures of two or more agents, can be used to improve foaming. The loading range of nucleating agent is from 0.01% to 1%, preferably from 0.05% to 0.6%, most preferably from 0.1% to 0.5%.
Compounding of the blended compositions of this invention can be performed by standard means known to those skilled in the art. Examples of compounding equipment are internal batch mixers, such as a HAAKE™, BANBURY™ or BOLLING™ internal mixers. Alternatively, continuous single or twin screw mixers can be used, such as a FARREL™ continuous mixer, a WERNER and PFLEIDERER™ twin screw mixer, or a BUSS™ kneading continuous extruder. The type of mixer utilized, and the operating conditions of the mixer, can affect properties of the composition such as viscosity, volume resistivity, and extruded surface smoothness.
The compounding temperature for the blends of this invention is typically from 170° C. to 200° C. to ensure the complete reaction of peroxide with HDPE/LDPE polymer blend, more typically from 180° C. to 190° C. The various components of the final composition can be added to and compounded with one another in any order, or simultaneously, but typically the HDPE and LDPE are first compounded with one another and then the peroxide and, if present, the CO2-philic compound are added either one before the other or simultaneously. Alternatively, the CO2-philic compound and/or peroxide are first formulated into a masterbatch with either or both the HDPE and LDPE as the carrier resin and then the masterbatch is added to the HDPE/LDPE blend. In embodiments where the peroxide is formulated into a masterbatch or otherwise compounded with one or more components prior to inclusion in the final formulation (“preblend”), the masterbatch or peroxide-containing preblend should be prepared at a temperature below the activation temperature of the peroxide to avoid peroxide decomposition prior to preparation of the final formulation. For example, when dicumyl peroxide is employed, preparation of a peroxide-containing masterbatch or preblend should be performed at temperatures below about 145° C.
In one embodiment, the HDPE/LDPE blends of this invention are contacted with CO2 under typical extrusion conditions and foamed at the same time that the insulation is being extruded onto the conductor. As the compound exits the extrusion die, pressure drop results in foaming by the dissolved gas. Methods for extrusion foaming are well known in the art.
Gel Content
About 1.5 grams (g) crosslinked samples are weighed and then packaged with metal net with the 180 meshes. The weights of sample before and after packaged are recorded. The packaged samples are inserted in a 250 mL flask and then immersed with 200 mL toluene. After boiling at 120° C. for at least 6 hours, the packaged samples are removed from the flask and dried at room temperature for 24 hours. The remnant weight is also recorded. Gel content is calculated by the equation:
where
W1 is weight after packaged with metal mesh;
W2 is weight before packaged with metal mesh; and
W0 is weight of initial sample.
Cell Size Analysis
The PE foam sample is fractured utilizing liquid nitrogen and then coated with Iridium. Scanning Electron Microscopy (SEM) images (
Density
Foam densities are measured according to ASTM D792-00 involving weighing polymer foam in water using a sinker.
Dissipation Factor (Df)
Dissipation Factor measurements are conducted on a High Frequency Split Post Dielectric Resonator at a frequency of 2.47 gigahertz (GHz) on 50 mil compression molded plaques. Before measurements, the plaques are conditioned for 24hours at room temperature (21-24° C.) in a desiccant chamber.
Porosity
Porosity is calculated based on the density of sample before and after foaming. The density of the foamed article and solid plaque are measured according to ASTM D792.
Porosity=(1−υfoam/υsolid)*100%
Tables 1 and 2 report the materials used in these examples.
Compounding
HDPE, LDPE, peroxide and PDMS are separately weighed into a beaker according to the formulation in Table 2, and then blended with one another to form a relatively homogeneous mass.
HAAKE ™ mixing equipment[from Thermo Scientific as HAAKE ™ Polylab OS, 50 cubic centimeter] having two sigma rotors rotating in opposite directions is pre-heated to 180° C.
The mixture of HDPE, LDPE, peroxide and PDMS is added to the mixer through the mixer filling port, and then blended at 180° C. for 8 minutes. The rotation rate of is 60 revolutions per minute (rpm).
When the blending is completed, the resulting mixture is withdrawn and cut into small pellets, ready for compression molding.
Preparation of Polyethylene Plates
The mixed PE pellets are placed into a mold in a hot plate compression molding machine, e.g., Platent Vulcanizing Press, manufactured by Guangzhou NO.1 Rubber & Plastic Equipment Co. Ltd., preheated to 150° C., held for 5 minutes and then subjected to compression pressure for 10 minutes. The resulting plate is cooled to room temperature (21-24° C.) and stored for the foaming experiments.
Sample Foaming
Samples are made using a batch foaming apparatus that is intended to represent a laboratory screening test that correlates with extrusion foaming during the wire coating process. The process comprises the steps of loading, preheating, saturating and depressurizing.
As shown in
Table 3 reports the processing conditions for both the comparative examples and inventive examples. Various measured sample properties are also reported in Table 3.
The dissipation factor of the foam extrudate is calculated using Equation 1.
Equation 1 is cited in Electrical Properties of Polymer: Chemical Principles, Hanser Publishers, 1976
For example, the calculation of the dissipation factor for the foam extrudate of Control 2 is:
Thus dissipation factor tan δγ=0.000037686.
As another example, the calculation of the dissipation factor for the foam extrudate of Example 2 is:
Thus dissipation factor tan δγ=0.000030475.
Percentage of Df improvement after foaming is calculated by comparing with that of Control 2 (0.00011) without foaming as follow:
In one embodiment the invention is peroxide selection for PE polymer resin system modification which has minimum deterioration on the DF property. Compared to DCP (control 5, DF of 57*10-5) and L101 (control 6, DF of 44*10-5), DTAP modified HDPE/LDPE blend has the lowest DF data, ca. 12*10-5 (Ex.2) when peroxide loading is 0.1% for all formulations.
As seen in Table 3, for pure HDPE resin and HDPE/LDPE=70/30, their porosity foamed by CO2 at 127° C. is 76% and 75%, respectively. Under these foaming conditions, the porosity of the HDPE/LDPE blend hardly improves although the LDPE is mixed with HDPE. In Control 3 and Control 4, the introduction of PMX-200 slightly increases the porosity relative to Control 1 and Control 2. Moreover, their pore sizes also clearly decrease. This is because PDMS is a CO2-philic compound and its addition can improve the CO2 solubility in PE resins.
In Ex. 1, the addition of DTAP peroxide into the HDPE/LDPE blend under the same reaction conditions in the HAAKE™ mixer did bring an increase in porosity. Its porosity reached 82%, moreover, its pore size decrease to less than 10 microns (seen in
With an increase in the amounts of DTAP and PMX-200, the porosity of the peroxide-modified samples also increase. The highest porosity is reported in Ex.4. Of note is that when the amount of PMX-200 is increased to 2%, pore size clearly increases relative to that which is achieved with 1% of PDMS 200.
The Df data of the comparative examples and several of the inventive examples are also listed in Table 3. For Control 1 and 2, the Df data are 7*10-5 and 11*10-5, respectively. The introduction of LDPE resulted in a Df increase. The effect of PMX-200 and different peroxides such as DCP and L101 on Df is also reported. When 1% PMX-200 is added into the blend of HDPE/LDPE, the Df of blend increases from 11*10-5 to 20*10-5 When 2% PDMS is added into the neat HDPE, the Df increases from 7*10−5 to 23*10−5. By comparison, DTAP with the same amount (0.1%) hardly results in a negative impact on the Df of the resin of Example 2, i.e., 12*10-5. When adding 1% PMX-200, the Df increased to 18*10-5 (Ex. 3). By theoretic estimation as shown in
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2015/096250 | 12/3/2015 | WO | 00 |
