Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B1/00—Dumping solid waste
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2310/00—Masterbatches

Definitions

• the present invention relates to geomembrane liners, and more specifically to geomembrane liners prepared using a special base resin and a special master batch allowing the geomembrane liners to operate at elevated temperatures up to 100°C.
• Stage 1 "ductile failure,” occurs due to stress overload and is a purely mechanical failure.
• Stage 2 "brittle-mechanical failure,” occurs due to creeping and depletion of additives.
• Stage 3 "brittle-chemical failure,” occurs due to complete consumption of additives; is purely chemical and independent of stress. Stage 3 failure is rapid.
• Stage 1 is dependent on the number and entanglement of tie-molecules. Resins with higher number of tie-molecules and more entanglements will have a longer ductile mode. At high temperatures, molecules are very active and mobile, which in turn accelerates the creeping mechanism. In addition, the rate of depletion of additives is also increased with the increase of temperature. The combined effects of creep and additives depletion Sower the lives of stages 2 and 3.
• compositions for preparing a geomembrane iiner for a containment system wherein said composition is of: 1) a master batch; and 2) a base resin and wherein said composition comprises:
• a master batch composition comprising: a) about 70 to about 80 wt% of one or more of a Linear Low Density Polyethylene (LLDPE), Medium Density Polyethylene ( DPE), High Density Polyethylene (HOPE), or Polyethylene of Raised Temperature (PERT) resin carrier has density from 0.910 to 0.955 g/cm 3 ;
• LLDPE Linear Low Density Polyethylene
• DPE Medium Density Polyethylene
• HOPE High Density Polyethylene
• PROT Polyethylene of Raised Temperature
• a primary antioxidant comprises 1 ,3, trimethyl-2,4,6-tris- ⁇ 3,5-di-t-butyl-4-hydroxybenzyl) benzene
• a secondary antioxidant comprises pentaerythritol tetrakis(3-(3,5-di-tert-butyi- 4-hydroxyphenyj)propionate);
• UV stabilizer comprises a high molecular weight hindered amine light stabilizer
• g about 20 to about 30 wt% of a carbon black, wherein said carbon black is a furnace carbon black, and wherein the percentages by weight add up to 100% and are based on the total weight of the master batch composition; and 2) about 90 to about 92 wt% of a base resin composition comprising a Poiyethy!ene of Raised Temperature (PERT) base resin, wherein the percentage by weight is based on the total weight of the geomembrane composition.
• PERT Raised Temperature
• resin carrier is one or more of a Linear Low Density Polyethylene (LLDPE), Medium Density Polyethylene (MOPE), High Density Polyethylene (HDPE), or Polyethylene of Raised Temperature (PERT).
• LLDPE Linear Low Density Polyethylene
• MOPE Medium Density Polyethylene
• HDPE High Density Polyethylene
• PROT Polyethylene of Raised Temperature
• the high molecular weight hindered amine light stabilizer is 1 ,3 s 5 ⁇ Triazine ⁇ 2,4,6-
• the acid neutralizer comprises hydrotalcite.
• a geomembrane iiner is provided, wherein this geomembrane liner is prepared by letting down the inventive composition (i.e., a master batch) in a base resin.
• the geomembrane iiner comprises about 1100 to about 1400 parts per million (ppm) of said primary antioxidant: about 400 to about 500 ppm of said secondary antioxidant;; about 0 to about 100 ppm of tris (2,4-di-tert-butylphenyl) phosphite; about 1200 to about 1500 ppm of said UV stabilizer: about 300 to about 400 ppm of said acid neutralizer; and about 20,000 to about 25,000 ppm of said carbon black.
• ppm parts per million
• Figure 1 illustrates the results of a hoop stress test of polyethylene of raised temperature (PE-RT) per ISO9080
• the invention provides geomembranes that are resistant to environmental stress crack, have good mechanical properties, and therefore can have long service lives at elevated temperatures of up to 100 °C,
• Base resin used in the inventive geomembranes is Polyethylene of Raised Temperature (PERT), which comprises disproportionately more high molecular weight particles than low molecular weight particles.
• PTT Raised Temperature
• most of the co- monomers (side branches) also have a relatively high molecular ⁇ /eight.
• a master batch is first prepared.
• the master batch can then be let down in the resin material to make a geomembrane. it is well within a skill of the art to prepare a final product (e.g., a geomembrane) from a master batch.
• the inventive master batch comprises a resin carrier; a carbon black; a thermal stabilizer which comprises a primary antioxidant, a secondary thermal stabilizer; and optionally, a tertiary antioxidant; a UV stabilizer; and an acid neutraiizer.
• resin carriers used in the inventive geomembranes comprise either Linear Low Density Polyethylene (LLDPE), Medium Density Polyethylene (MDPE), or High Density Polyethylene (HOPE),
• LLDPE Linear Low Density Polyethylene
• MDPE Medium Density Polyethylene
• HOPE High Density Polyethylene
• the resin carriers comprise Polyethylene of Raised Temperature (PERT).
• PERT resins for the purposes of this invention include Dowlex® 2344, Dowlex® 2377, Dowlex® 2388, DGDA-2399, intrepidTM 2498 NT, IntrepidTM 2499 NT (ali products of Dow Chemical, US), Yuclair® DXBOO (SK Global Chemical, South Korea), Daelim XP9000 (Daelim, South Korea), Total XRT70 (Total, France), Hostaien 4731 B (LyondellBasell, the Netherlands), and E!tex® TUB220-RT (Sneos, Switzerland).
• Non-PERT resins also can be used as carriers.
• High Temperature Liner incorporated non-PERT Master batch has an application limit of 90 °C.
• Some non-!imiting trade name of preferred non-PERT resins for the purposes of this master batch invention include SABIC® LLDPE 0132HS0G (Saudi Basic Industries Corporation, Saudi Arabia), Marlex® K203 (Chevron Phillips Chemical Company, US), and Dowlex® 2342 (Dow Chemical, US).
• Resin carriers used for this master batch invention should have density from 0.910 to 0.955 g/cm 3 ; and Melt Index (Ml) (2.16kg) of less than or equal to 1 dg/min.
• the thermal stabilizer used in the inventive compositions comprises a primary antioxidant, a secondary thermal stabilizer; and optionally, a tertiary antioxidant.
• the primary antioxidant is used for long term stabilization and comprises 1 ,3, trimethyl-2 ,4 ,6-tris-(3 , 5-di-t-buty!-4 ⁇ hyd roxybenzyl) benzene, CAS No. 1709-70-2.
• Some non-limiting trade name examples of the primary antioxidant include irganox 1330 (BASF, Germany), Ethanox 330 (Albemarle Corporation, US), BNX 1330 (Mayzo, US), Songnox 330 (Songwon, South Korea), and others.
• the secondary antioxidant used in the inventive compositions is a hindered pheonolic antioxidant called pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxypheny!prDpionate, CAS No. 6683-19-8.
• Some non-limiting trade name examples of the secondary antioxidant include Irganox 1010 (BASF, Germany), BNX 1010 (Mayzo, US), Songnox 1010 (Songwon, South Korea), and others.
• the tertiary antioxidant that can optionally be used in the inventive compositions is an organophosphite. Sn one aspect, this organophosphite is tris (2,4-di- tert-butylphenyf) phosphite, CAS No. 31570-04-4.
• organophosphite is tris (2,4-di- tert-butylphenyf) phosphite, CAS No. 31570-04-4.
• Some non-limiting trade name examples of the tertiary antioxidant include Irgafos 168 (BASF, Germany), Benefos® 1880 (Mayzo, US), Songnox 1680 (Songwon, South Korea), and others.
• the UV stabilizer used in the inventive compositions comprises a high molecular weight hindered amine light stabilizer (HALS).
• HALS high molecular weight hindered amine light stabilizer
• this HALS is 1 j 3 ) 5-Triazine-2,4,6-triamine,N,N , ' ⁇ 1 J 2-ethane-diyi-bis[[[4 ) 6-b!s[butyin,2,2,6,6- pentamethyl ⁇ -piperidinyl aminoj- ⁇ -triazine ⁇ -ylliminoJ-S -propanediy!]].
• Some non- limiting trade name examples of the UV stabilizer include Chimassorb 19 (BASF, Germany), Sabo® Stab UV 119 (Sabo S.p.A, Italy), Lowilite® 19 (Chemtura, US), and others.
• the acid neutralizer used in the inventive compositions comprises hydrotalci ' te, CAS No. 11097-59-9.
• Some non-limiting trade name examples of the acid neutralizer include DHT-4A (Kisuma Chemicals, the Netherlands), DHT-4V (Kisuma Chemicals, the Netherlands), Hycite® 7 3 (Teiko, Finland), and others.
• the carbon black used in the inventive compositions has a particle size smaller than or equal to a particie size of N680 carbon black.
• Some non-limiting trade name examples of the carbon black include Arosperse 5 (Orion Engineered Carbons, US), Raven® 880 Ultra (Columbian Chemicals, US), Black Pearls® 4060 (Cabot Corporation, US), and others.
• a composition for preparing a geomembrane liner for a containment system wherein said composition is of: 1) a master batch; and 2) a base resin and wherein said composition comprises: 1 ) about 8-10 wt% of a master batch composition comprising: a) about 70 to about 80 wt% of one or more of a Linear Low Density Polyethylene (LLDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE), or Polyethylene of Raised Temperature (PERT) resin carrier has density from 0.910 to 0.955 g/cm 3 ; b) about 1 to about 3 wt% of a primary antioxidant, wherein said primary antioxidant comprises 1 ,3, trimethyi-2,4 I 6-iris-(3,5-di-t-butyi-4-hydroxybenzyl) benzene;
• LLDPE Linear Low Density Polyethylene
• MDPE Medium Density Polyethylene
• HDPE High Density Polyethylene
• PROT Polyethylene of
• secondary antioxidant comprises pentaerythritol tetrakis(3-(3,5-di ⁇ tert-butyl- 4-hydroxyphenyl)propionate);
• UV stabilizer comprises a high molecular weight hindered amine light stabilizer
• resin carrier is a Linear Low Density Polyethylene (LLDPE), Medium Density Po!yethyiene (MDPE), High Density Poiyethylene (HDPE), o Polyethylene of Raised Temperature (PERT).
• the acid neutraiizer comprises hydrotalcite.
• a geomembrane liner is provided, wherein this geomembrane liner is prepared by letting down the inventive composition (i.e., a master batch) in a base resin.
• the geomembrane iiner comprises about 1100 to about 1400 ppm of said primary antioxidant; about 400 to about 500 ppm of said secondary antioxidant; about 0 to about iOOppm of trss (2,4-di- tert-buty!phenyl) phosphite; about 1200 to about 1500 ppm of said UV stabilizer; about 300 to about 400 ppm of said acid neutraiizer; and about 20,000 to about 25,000 ppm of sa id carbon black.
• the total amount of the primary antioxidant, the secondary antioxidant, tris (2,4-di-tert-buty!phenyi) phosphite, the UV stabilizer, and the acid neutraiizer is preferably between about 3000 and 3800 ppm.
• Geomembranes of the invention can be used for various purposes known to those skilled in the art. Such purposes include, but are not limited to, lining landfills, hot water containments, underground thermal energy storage, heap leach pad mines, industrial fluid discharges, and the like. This preceding list of possible uses is not limiting and is not intended to limit the applicability of the provided compositions in any way.
• Table 1 lists the ingredients of one of the inventive compositions (an example of a master batch).
• Wastes-batch Formula %
• Table 2 lists the ingredients of one of the inventive compositions (an example of a geomembrane).
• OIT Oxidative Induction Time
• HPOIT High Pressure OIT
• Test results are shown in Table 3 to Table 6.
• TabSe 3 GMRT 1/ 85°C Oven Aging
• Atmospheric Oxygen pressure (OIT - minute) 116 82 71 %
• GMRT 1 and G RT 2 samples were tested for tensile properties according to ISO 527-1, 2. Young's Moduius of 35 MPa, Tensile Yield Stress of 4 MPa, and Break Tensile Elongation of 400% are arbitrarily chosen as minimum values to assure integrity of solid state property of Geomembrane at an elevated temperature. Results are shown in Table 10 and Table 11.
• PE-RT Polyethylene of Raised Temperature resin used as the base resin for the high temperature liner has a history of successful field service for high temperature pressure pipes applications.
• Fig, 1 illustrates the results of a USO9080 hoop stress test of PE-RT.
• Such hoop stress test is a typical test method to evaluate the creep resistance of pressure pipes, and gives an extrapoiating method of linear regression analysis to estimate the lifespan of a resin in pipe form.
• the PE-RT was tested for hoop stress test at four temperatures: 20, 80, 95, and 110°C. At 110°C testing temperature, no creep failure was observed after 10,000 hours (over 1 year) testing. Through the extrapoiating method, the resin is determined to have over 25 years creep resistance at 80°C.
• Exposure cycle 20 h UV cycle at 75°C followed by 4 h condensation at 80°C
• UV Iamp UVA-340
• Irradiance level 0.72 W/(m 2 .nm) at 340 nm
• Tensile properties of the high temperature liners are shown in Table 13 and 14.
• Table 13 compares the tensile properties at room temperature of the high temperature liners (60 mil) versus industry regulation (GRI GM13) per ASTM D6693
• Table 14 shows the advantageous tensile properties at high temperatures of the inventive high temperature liners (60 mil) per ISO 527.
• a geomembrane meeting the following criteria will function well as a solid barrier by assuring the integrity of its solid state property at an elevated temperature:
• Elastic modulus also known as tensile modulus, is a measure of the stiffness of materials. Coupled with yield stress and break tensile elongation, it tells the mechanical integrity of the geomembrane at the test temperature.
• Elastic Modulus of the high temperature Liner at 100°C is higher than 38 MPa (5,500 psi). This value is comparable to those of VLDPE and TPO roofing membranes at room temperature.
• NCTL Notched Constant Tensile Load
• NCTL (Eg 50°C 300 hrs ⁇ 2000 hrs

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• 2014
  • 2014-05-06 US US14/271,011 patent/US9518176B2/en active Active
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