KR101187858B1 - Geotechnical article and process for forming it - Google Patents

Abstract

A geotechnical article and a method of making the article, the article having a coefficient of thermal expansion of less than about 150 ppm / ° C. at ambient; Resistance to acidic media larger than polyamide 6 resin and / or resistance to basic media larger than PET resin; Resistance to hydrocarbons greater than HDPE; Creep coefficient of at least 400 MPa (ISO 899-1) at 25 ° C., 20% yield stress and 60 min load time; And at 25 ° C., having a 1 percent secant warpage coefficient of at least 700 MPa (ASTM D790; the article comprises (a) from about 1 to about 95 weight percent of at least one functional group-containing polymer or oligomer; and (b) at least one Compositions comprising about 5 to about 99 weight percent of the engineering thermoplastics, and optionally containing fillers, optionally containing unmodified polyolefins, ethylene copolymers or ethylene terpolymers.

Description

TECHNICAL ARTICLE AND PROCESS FOR FORMING IT

Cross Citation for Related Applications

This application is simultaneously filed and entitled US Patent Application No. (PRSI 200002) entitled “UV Resistant Multilayer Cellular Confinement System”; US Patent Application No. (PRSI 2000003), filed simultaneously and entitled "Geological Engineering Articles"; United States Provisional Patent Application No. (PRSI 200005), filed simultaneously and entitled "Welding Methods and Civil Engineering Products thereof"; And US Provisional Patent Application No. (PRSI 200006), filed simultaneously and entitled "Method of Making a Compatibilized Polymer Blend." These four patent applications are incorporated herein by reference in their entirety.

The present invention relates to high efficiency civil composite articles such as reinforcing strips, reinforcing components, membranes and especially dimensional stable cellular restraint systems. The present invention relates in particular to civil engineering articles formed from or comprising commercially available polymer compositions and characterized by structures and compositions adapted to provide improved properties.

Plastic geotechnical reinforcement components and articles, in particular cellular restraint systems (CCS), are made from soil, rock, sand, stone, peat, clay, concrete, aggregate, road building materials and soils supported by the CCS. It is used to increase the load bearing capacity, stability and corrosion resistance of geotechnical reinforced materials, such as earthen materials.

CCS is mostly made from strips comprising high density polyethylene (HDPE) or medium density polyethylene (MDPE) and is characterized by a honeycomb three-dimensional cell structure. The structure includes, for example, soil, rock, sand, stone, peat, clay, concrete, aggregate, road construction and other soil-made materials, or mixtures of these and / or other materials such as fluids contained within the material. When filled with a geotechnical material, it provides reinforcement and stability to both the geotechnical material and the surrounding structure.

The CCS strengthens the GRM by increasing the shear force and stiffness of the GRM as a result of the hoop strength of the cell wall, the passive resistance of the adjacent cell and the friction between the CCS and the GRM. Under load, the CCS produces strong lateral confinement forces and soil-cell wall friction. This mechanism creates a bridge structure with high flexural strength and rigidity. This bridging action improves the long-term load-strain characteristics of conventional granular fillers and allows for a dramatic reduction in the thickness and weight of the structural support component by 50%. CCS can be used in load-bearing applications such as road foundation stabilization, integrated transport yards, railroad tracks to stabilize track gravel, on retaining walls to protect GRM or vegetation, and also on slopes and channels. .

The term "HDPE" refers to polyethylene resin specified below at a density of 0.941 to at least 0.960 g / cm 3, and the term "MDPE" refers to polyethylene resin specified at a density of 0.926 to 0.940 g / cm 3.

Reinforced CCS is a composite structure wherein the GRM is compressed and densified against the CCS wall, and the friction between the wall and the GRM keeps the structure in shape. The plastic cell and GRM infill support each other mechanically and must be able to withstand under varying spectra loads, vibrations, impact loads, thermal stresses and corrosion.

Three major factors affecting the long-term effective durability of the GRM-CCS composite structure are: (1) creep resistance of plastic materials; (2) friction between the cell wall and a geotechnical reinforcement (GRM) stabilized and strengthened within the CCS; And (3) dimensional stability of the compact GRM and CCS.

Creep on the CCS wall weakens friction and loses the structural functionality of the CCS-GRM composite. HDPE and other polyolefins failed to withstand creep, particularly at temperatures above about 35-40 ° C. The situation is much worse for MDPE.

The possibility of heating geological articles, especially CCS, is largely associated with hot areas of the world. As used herein, in one embodiment, the term “hot area” refers to an area located within 42 ° on either side (north or south) of the earth's equator. In one embodiment, “hot area” refers to an area located within 30 ° on either side of the earth's equator. In particular, hot areas include areas within and near the desert belt. For example, parts of North Africa, southern Spain, the Middle East, Arizona, Texas, Louisiana, Florida, Central America, Brazil, India, South China, Australia, and Japan can be considered hot areas. In general, these hot areas regularly experience temperatures above 35 ° C, or even above 40 ° C. The surface of the plastic article exposed to direct sunlight can reach temperatures of 75 ° C., even 90 ° C.

The failure mechanism of CCS at elevated temperatures can be complex. The first step is to heat the GRM surface and the exposed CCS surface, in particular by absorbing sunlight. An increase in the CCS temperature results in a change in dimension, because polyethylene (PE) has a high coefficient of thermal expansion (CTE) (about 150-200 ppm / ° C), and the CTE itself increases in temperature Because it actually increases with. This means that when 100 meters (m) of CCS is heated from 25 ° C. to 65 ° C., its length will increase by about 60-80 cm. Since the GRM accommodated by the CCS expands much smaller, the coupling between the GRM and the CCS, i.e., the ability of the CCS to accept the GRM worsens. In addition, when CCS is exposed to heat for several hours a day, the exposure leads to creep and irreversible expansion. As a result, the intimate contact between CCS and GRM will be irreversibly reduced even when the temperature drops, thus reducing or even eliminating the integrity and efficiency of the combined structure. Thus, repeated heating cycles, expansion of the CCS, and consequently the unfolding and collapse of the GRM structure pre-incorporated in the CCS result in a final failure or significant loss of CCS functionality.

The situation is exacerbated during the fall and winter when GRM undergoes freezing and greening of water, which is the process that causes GRM to expand to CCS. Since creep resistance of HDPE and MDPE is medium or much lower, the result is a further loss of contact between the CCS wall and the GRM. This occurs naturally, for example, because of freezing and melting cycles, which push stones out of the soil in winter, or for example, water freezes in cracked concrete or rock to break concrete or rock.

The shear surface of the CCS structure, usually the surface of each cell, is embossed or provided with other friction-reinforcing means, increasing the friction with the GRM and preventing the deformation of the walls, thereby rupturing the original appearance of the composite structure. You can prevent it.

Commercially available HDPE-based CCSs are characterized by moderate stiffness, moderate dimensional stability, and acceptable creep resistance at temperatures ranging from about -10 ° C to 40 ° C. However, these CCSs are characterized by several drawbacks: they have moderate strength, high CTE, high creep tendency, and chemical sensitivity to hydrocarbons, more particularly fuels and oils, especially at temperatures above 40 ° C. .

Chemical susceptibility to hydrocarbons means that the CCS or membrane is in contact with fuel or oil, for example, for strengthening or confining GRM in landfills, oil fields, gas stations, intensive parking areas, and the chemical industry, or as barriers in landfills and reservoirs. It is harmful when applied where it becomes.

The limited mechanical and chemical properties of HDPE and MDPE, as well as other polyolefins, are particularly related to creep resistance and limited thermal resistance, as well as a high tendency to expand when exposed to hydrocarbon fluids. If one compares the creep resistance and chemical resistance to hydrocarbon fluids under the same load, between engineering thermoplastics (ET), such as polyamide or polyester and the other, the engineering thermoplastic is much more. It is dimensionally stable and rigid, has a lower creep tendency, has higher chemical resistance and higher strength to fuels and organic fluids.

In contrast to the above ET, polyethylene has better tear and puncture resistance than engineering thermoplastics, especially at temperatures below 0 ° C. Tear strength and puncture resistance are important issues for membranes and CCS, and even more important for perforated CCS, penetration provides drainage through plastic walls, but weakens the strip and increases the sensitivity of the strip to tearing. Tear and puncture resistance is also important in the installation process where the CCS is still empty prior to charging with GRM and needs to withstand human activities related to installation and GRM charging.

The advantages of such engineering thermoplastics are even greater when comparing properties at temperatures above about 40-50 ° C. Since most CCSs are manufactured by welding a plurality of strips, the weld strength and weld formation rate are better in engineering thermoplastics than in HDPE or MDPE. Another advantage of engineering thermoplastics based CCS compared to polyolefins is the improved coefficient of friction with GRMs, especially soils and peat, due to their high polarity. Engineering thermoplastics are also more resistant to expansion by hydrocarbons such as fuels and oils.

The main limiting factors of engineering thermoplastics in choosing CCS resins are: high modulus of elasticity, relatively high cost, relatively high sensitivity to acids and bases, relative to temperatures below about 10 ° C, affecting installation simplification. Low melt strength that affects brittleness and simplification of strip extrusion.

Combining engineering thermoplastics and polyolefin resins in one blend is disclosed in several prior art patents.

U. S. Patent No. 3,963, 799 provides a process for forming compositions of polyamides and polyolefins and mixtures thereof (commercialized blends) that are generally used in the packaging industry. The compositions disclosed in this patent are not applicable to structural geotechnical applications, including CCS, in particular because they are not protected against inherent brittleness and moisture and UV light at low temperatures. The patent does not address the difficulties in welding the composition, but the hydrolysis instability of the polyamide phase, which can be hydrolyzed in soil, particularly acidic soils. In addition, the compositions of this patent have too high CTE for CCS and membranes.

U. S. Patent 4,564, 658 provides a composition only of polyester and linear low density polyethylene (LLDPE) and does not provide a compatibilizer, i.e., a formulation for stabilizing a dispersion of two unmixed polymers. As a result, the melt flow is non-uniform (melt fracturing) in application to extrusion, such as extrusion of strips for geotechnical applications, and separation between phases is observed. The compositions disclosed in this patent are not applicable to structural geotechnical applications including CCS because of their flexibility and cleavage tendencies. Due to the properties of LLDPE, the compositions of this patent have too high CTE for CCS and membranes.

The patent also does not provide a solution for protecting the blend from hydrolysis in soil and landfills, oils and hydrocarbons, and degradation induced by heat and UV light. The quality of the weld is not discussed.

U. S. Patent No. 5,280, 066 provides a composition of polyesters, polyolefins and functional styrene elastomers, in particular for injection molding, for improving impact resistance. The invention is limited to polyolefin fractions only with polypropylene (PP). PP is too rigid and inflexible at temperatures below about 0 ° C., which is an essential characteristic in CCS. The compositions of this patent have too high CTE for CCS and membranes.

The compatibilizer according to this patent is styrene-based and therefore has a limited UV light resistance, thus limiting the lifetime of the composition to about 1 to 2 years for indoor and outdoor applications. Polyester blends can lose their function in a relatively short period of time, especially in soils, especially soils with a pH of 7 or more, when not particularly stabilized against hydrolysis. The patent does not provide sufficient protection against oils and fuels, acids and bases and UV light. The quality of the weld is not discussed.

US Pat. No. 6,875,520 provides a composition of polyamide block copolymers and polyolefins that are highly flexible. The invention may be useful for flexible geomembrane but not for structural geotechnical applications including CCS and high efficiency membranes. High flexibility, which is an advantage in flexible geomembrane, is a drawback in CCS: When a load is applied to a CCS supporting GRM, the two-component composite structure interacts with the load as an integrated system. CCS transfers load from cell to cell by friction with GRM, which provides strength and stiffness. If the CCS is too flexible, the load induces deformation of the CCS until the friction with the GRM is low. In this particular state, the integrated system is irreversibly damaged and can no longer provide the required durability, stiffness and stability to GRM. The patent does not provide a solution for the hydrolysis of the composition in soil and landfills or upon exposure to concrete or other media characterized by a pH of 7 or greater. The compositions of this patent have too high CTE for CCS and membranes.

UV and thermal stability, especially for longer than two years, required in CCS is not discussed or provided.

Thus, creep resistance, wider strength and stiffness, lower CTE and lower tendency to lose stiffness at elevated temperatures, such as temperatures ranging from -70 ° C to 90 ° C, freezing / recording / heating process of GRM Higher resistance to creep during, greater resistance to swelling by low molecular weight substances such as oils and hydrocarbons, UV light in a wide spectrum of climatic ranges from dry to polar regions for a period of about 2 to about 100 years; It is characterized by greater resistance to pyrolysis and improved properties such as one or more of improved weld strength and weld load bearing resistance, and in particular the long need for providing improved polymer compositions compared to HDPE and MDPE. This exists. Such improved polymer compositions would be desirable as CCS for high efficiency applications and CCS for GRM enhancement comprising oils, acids and bases, aggressive chemicals, solvents and fuels. There is also a need for improved geotechnical articles, such as geomembranes and geogrids, with improved properties important for the application in which the articles are placed. The need for such compositions and materials produced therefrom remains unmet so far.

Short description

According to one embodiment of the present invention, there is provided a geotechnical article comprising at least one layer, the at least one layer having a coefficient of thermal expansion of less than about 150 ppm / ° C at ambient temperature; Resistance to acidic media larger than polyamide 6 resin and / or resistance to basic media larger than PET resin; Resistance to hydrocarbons greater than HDPE; A tensile creep coefficient of at least 400 MPa according to ISO 899-1 (hereinafter referred to as “creep coefficient”) at 25 ° C., a load of 20% yield stress and a load time of 60 minutes; And at 25 ° C., has a 1 percent secant flexural modulus of at least 700 MPa according to ASTM D790; The at least one layer is:

(a) from about 1 to about 94.5 weight percent of a composition or polymer comprising at least one functional group-containing polymer or oligomer, on average comprising at least one functional group per molecule, wherein the at least one functional group is a carboxyl, anhydride, oxirane, Amino, amido, ester, oxazoline, isocyanates or any combination thereof;

(b) from 5 to about 98.5 weight percent of the at least one engineering thermoplastic;

(c) from about 0.5 to about 94 weight percent of at least one filler; And

(d) Optionally, a composition may be formed comprising up to about 93.5 weight percent of an unmodified polyolefin, ethylene copolymer or ethylene terpolymer.

In any composition or article of the present invention, the filler may be in the form of a powder, whisker or fiber, having an average particle size of less than about 30 microns in the form of a powder. In any composition or article of the invention, the content of (b) may be from about 90% to about 10% by weight. In any composition or article of the invention, the at least one filler of (c) is a metal oxide, metal carbonate, metal sulfate, metal phosphate, metal silicate, metal borate, metal hydroxide, silica, silicate, aluminate, Alumino-silicates, chalk, talc, dolomite, organic or inorganic fibers or whiskers, metals, metal-coated inorganic particles, clays, kaolin, industrial ash, concrete powders, Cement, dolomite, wollastonite or mixtures of any two or more thereof.

In any composition or article of the invention, the at least one engineering thermoplastic material is selected from (i) a polyamide; (Ii) polyester; (Iii) polyurethane; Or a copolymer, block copolymer, blend or combination of any two or more of (iii), (ii) and (iii).

In any composition or article of the invention, the polymer or oligomer containing the functional group may be a polymer or terpolymer of (1) at least one unsaturated monomer and (2) an unsaturated monomer containing at least one functional group, and Unsaturated monomers containing functional groups include at least one unsaturated group and at least one such functional group.

In any composition or article of the invention, the polymer or oligomer containing at least one functional group is selected from maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-acrylic acid or methacrylic ester esters. Polymer or terpolymer, maleic anhydride grafted propylene homopolymer or copolymer, maleic anhydride grafted ethylene-alpha olefin polymer, maleic anhydride grafted ethylene-propylene rubber, glycidyl methacrylate Or acrylate (GMA) grafted polyethylene, GMA grafted ethylene-acrylic acid or methacrylic ester copolymer or terpolymer, GMA grafted propylene homopolymer or copolymer, GMA grafted ethylene-alpha olefin polymer, GMA grafted ethylene -profile Rubber, acrylic or methacrylic acid grafted ethylene copolymers or terpolymers, acrylic or methacrylic acid ionomers, styrene-maleic anhydride copolymers or terpolymers, styrene-acrylic acid or styrene-methacrylic acid copolymers Or terpolymers, copolymers or terpolymers of ethylene-glycidyl methacrylate or ethylene-glycidyl acrylate, or combinations thereof.

In any composition or article of the invention, when the unmodified polyolefin, ethylene copolymer or ethylene terpolymer of (d) is present, polyethylene, ethylene-vinyl acetate, polypropylene, ethylene-alpha olefin elastomer, ethylene-propylene Independently from an elastomer, an ethylene-propylene diene elastomer, an ethylene-acrylate ester or methacrylate ester copolymer or terpolymer, or any copolymer or combination thereof.

In any composition or article of the invention, the composition further comprises a heat stabilizer, a hindered amine light stabilizer (HALS), an organic UV absorber, an inorganic UV absorber, a hydrolysis inhibitor, or a combination thereof. Can be.

In any composition or article of the present invention, the hydrolysis inhibitor may react with end groups or side groups of the at least one engineering thermoplastic, and may be carbodiimide, polycarbodiimide, block isocyanate, epoxy Resins, phenolic resins, novolac resins, melamine resins, urea resins, glycoluril resins, triisocyanuric acid and derivatives thereof, styrene-maleic anhydride resins, or aromatic or cycloaliphatic diacids or anhydrides thereof At least one selected from a ride.

In any composition or article of the invention, the composition may further comprise nano-sized particles characterized by barrier properties, the transmittance of the composition to molecules having a molecular weight less than about 1,000 Daltons At least 10% lower than compositions comprising the same composition except that there are no size particles.

In any of the compositions or articles of the invention, the nano-sized particles are nano-clay, nano-silica, nano-silicate, nano-alumosilicate, nano-zinc oxide, nano-titanium oxide, nano-zirconium oxide , Nano-talc, nano-tubes, nano-metal particles and / or flakes, carbon black, nano-sized sulfides and sulfates and nano-sized celluloses, lignin or proteins derived from plants or animals and any two of these It can be selected from the above combination.

In any composition or article of the invention, the article may comprise an extruded or molded strip having a thickness in the range of about 0.1 mm to about 5 mm. In any of the compositions of the present invention, the strip having the given size is 4 lb / between the strip and the sand as compared to the strip of given size formed of virgin MDPE or HDPE when tested by ASTM D6706-01. have a pullout force of at least 10% greater at a normal stress of in ² (about 27.58 kPa). In any of the compositions of the present invention, the strip may comprise a friction-promoting portion on at least one outer surface of the article, the friction-promoting portion being fabric, embossment, debossment, through-hole ( through-holes, finger extensions, hair extensions, wave extensions, coextrusion lines, bonded fibers or grains or aggregates, dots, mattes or any combination thereof.

In any of the compositions or articles of the invention, the geotechnical article may be a three-dimensional cellular restraint system (CCS) comprising a plurality of strips, each strip connected in parallel with its neighbors through separate physical seams. And the seams are separated from each other by non-joint regions. In any of the compositions of the present invention, the three-dimensional CCS is a blockade of a material made of soil, soil, rock, gravel, sand, stone, peat, clay, concrete, aggregate, road construction material and any combination of two or more thereof, and Suitable for confinement and / or strengthening. In any composition or article of the invention, the distance between the seams may range from about 50 mm to about 1,500 mm. In any composition or article of the invention, the seam may be provided by welding, bonding, sewing, stapling, riveting, or any combination thereof. In any composition or article of the invention, the seam may be welded by one or more of ultrasonic welding, laser welding, and thermopressure welding. In any composition or article of the invention, the welding may be required for at least 10% shorter welding cycle time compared to pure HDPE for the same weld dimensions. In any composition or article of the invention, where the seam is welded, the final weld strength of the two welded strips at ambient temperature is greater than about 1,300 N for a 100 mm weld width as measured at least 48 hours after welding. Can be large. In any composition or article of the invention, where the seam is welded, the final weld strength of the two welded strips at −20 ° C. is about 1,000 N for a 100 mm weld width as measured at least 48 hours after welding. Can be greater than In any composition or article of the invention, where the seam is welded, the final weld strength of the two welded strips at 70 ° C. is greater than about 1,000 N for a 100 mm weld width as measured at least 48 hours after welding. Can be large.

In any composition or article of the invention, where the two strips are joined by welding, when the welded joint is subjected to continuous load of 77 kg per 100 mm weld length for 10 days at ambient temperature, substantially As a result, all of the welded joints must remain intact.

In any composition or article of the invention, where the two strips are joined by welding, when the welded joint is subjected to continuous load of 77 kg per 100 mm weld length for 30 days at ambient temperature, substantially As a result, all of the welded joints must remain intact.

In any composition or article of the invention, where the two strips are joined by welding, when the welded seam receives a continuous load of 88 kg per 100 mm weld length for 20 days at ambient temperature, about At least 90% of the welded joints must remain intact.

In any of the compositions or articles of the invention, where the two strips are joined by welding, when the welded seam receives a continuous load of 88 kg per 100 mm weld length for 30 days at ambient temperature, At least 80% of the welded joints must remain intact.

In any composition or article of the invention, where the two strips are joined by welding, when the welded seam is subjected to a continuous load of 100 kg per 100 mm weld length for 10 days at ambient temperature, substantially As a result, all of the welded joints must remain intact.

In any of the compositions or articles of the invention, where the two strips are joined by welding, when the welded seam receives a continuous load of 100 kg per 100 mm weld length for 20 days at ambient temperature, At least 80% of the welded joints must remain intact.

In any of the compositions or articles of the invention, where the two strips are joined by welding, when the welded joint is subjected to a continuous load of 100 kg per 100 mm weld length for 30 days at ambient temperature, At least 60% of the welded joints must remain intact.

In any composition or article of the invention, where the two strips are joined by welding, when the welded seam receives a continuous load of 88 kg per 100 mm weld length for 30 days at -20 ° C, At least about 70% of the welded seams should remain intact.

In any composition or article of the invention, where the two strips are joined by welding, when the welded seam receives a continuous load of 88 kg per 100 mm weld length for 30 days at + 70 ° C., At least about 60% of the welded joints must remain intact.

In any composition or article of the invention, the article may further comprise a reinforcing structure suitable for attaching the article to a substrate.

In any composition or article of the invention, the composition or article may have a 1% secant modulus according to ASTM D790 of at least 600 MPa when measured at 45 ° C.

In any composition or article of the invention, the composition or article may have a 1% secant coefficient according to ASTM D790 of at least 500 MPa when measured at 70 ° C.

In any composition or article of the invention, the composition or article may have a 1% secant warpage coefficient according to ASTM D790 at least 10% greater than that of HDPE when measured at a temperature of about 45 ° C.

In any composition or article of the invention, the composition or article may have a 1% secant warpage coefficient according to ASTM D790 at least 10% greater than that of HDPE when measured at a temperature of about 70 ° C.

In any of the compositions or articles of the invention, the article has at least one additional layer applied to, coextruded, or laminated with the at least one layer. Can be. In any composition or article of the invention, the at least one additional layer may be (1) the same as or different from the composition of the at least one layer, wherein (a), (b) and (c) as defined above Composition), or (2) a material different from the composition comprising (a), (b) and (c). In any embodiment of the invention, the article may be a geomembrane.

In any such geomembrane, the geomembrane may comprise a plurality of sheets welded or joined together at each corner. In any such geomembrane, the geomembrane is (a) acid, base, oil, fuel, heavy metal, dioxin, oxygen, nitrate, sulfate, phosphate, SO _x , NO _x , compared to HDPE geomembrane having the same dimensions. Chlorofluorocarbons, organophosphorus compounds, herbicides, insecticides, fungicides, halogens, halogen acids, chlorine and its organic derivatives, bromine and its organic derivatives, ammonia, ammonium salts and organic derivatives, benzene and organic derivatives, toluene organic derivatives, phenolic organics Low permeability to one or more of derivatives, radioactive compounds, chemical warfare agents, bacteria, viruses, fungi, algae, and organic solvents, (b) having the same dimensions when exposed to fuels and hydrocarbons At least 10% more elastic modulus at 25 ° C. according to ASTM D790 compared to HDPE geomembrane; And (c) at least 10% higher creep coefficient at 20% yield stress and 60 minutes loading time when measured at 60 ° C. according to ISO 899-1, compared to HDPE geomembranes having the same dimensions. It may include a sheet having.

In any composition or article of the invention, at least one layer may provide 10% greater thermal conductivity compared to HDPE layers having the same dimensions.

In any composition or article of the invention, the at least one layer may further comprise an additive selected from HALS, organic UV absorbers or inorganic UV absorbers or any combination thereof, wherein the layers comprise the same additives and At least 10% lower extraction, evaporation and / or hydrolysis rates compared to HDPE layers having the same dimensions.

In any composition or article of the invention, the at least one layer may exhibit at least 10% lower weight gain than HDPE layers having the same dimensions after immersion in n-octane for 60 days at 25 ° C.

In any of the compositions or articles of the invention, the at least one layer is at least 10% better elongation at break compared to a polyethylene terephthalate (PET) layer having the same dimensions after immersion in an aqueous solution of pH = 11 for 60 days at 45 ° C. (elongation to break).

In any of the compositions or articles of the invention, the at least one layer may exhibit a retention of at least 10% better elongation at break as compared to a PA6 layer having the same dimensions after liver immersion in an aqueous solution of pH 4 for 60 days at 45 ° C. have.

In any composition or article of the invention, the composition may comprise a continuous phase and a discontinuous phase dispersed in domains throughout the continuous phase, wherein the substantially all of the regions are at most about 10 microns or less; Have large dimensions. In any composition or article of the invention, all of these regions may have a largest dimension of substantially less than or equal to about 3 μm.

In any composition or article of the invention, the geotechnical article may be CCS, geomembrane or geogrid.

According to one embodiment of the invention, there is provided a method for forming a geotechnical article comprising at least one layer, wherein the at least one layer is: at least one layer is about 150 ppm / ° C. at ambient temperature Thermal expansion coefficient below; Acidic medium resistance greater than polyamide 6 resin and / or basic medium resistance greater than PET resin; Higher hydrocarbon resistance than HDPE; A creep coefficient of at least 400 MPa according to ISO 899-1 at 25 ° C., at a load of 20% yield stress and a load time of 60 minutes; And a 1% secant warpage coefficient of at least 700 MPa according to ASTM D790 at 25 ° C .; The at least one layer is as described herein

(a) about 1 to about 94.5 weight percent of the composition of a polymer or oligomer comprising, on average, at least one functional group per molecule, wherein the at least one functional group is a carboxyl, anhydride, Oxirane, amino, amido, ester, oxazoline, isocyanate or any combination thereof;

(b) about 5 to about 98.5 weight percent of the composition of at least one engineering thermoplastic;

(c) about 0.5 to about 94 weight percent of the composition of at least one filler; And

(d) optionally, up to about 93.5 weight percent of the unmodified polyolefin, ethylene copolymer or ethylene terpolymer, wherein the process comprises

(Iii) providing a polymer or oligomer comprising at least one functional group of (a) and at least one engineering thermoplastic material of (b);

(Ii) melt kneading the combination of (a) and (b);

(Iii) adding at least one filler as in (c) and melt kneading by combining the (a), (b) and (c);

(Iii) optionally adding at least one unmodified polyolefin, ethylene copolymer or ethylene terpolymer of (d) to any of (a), (b) or (c) or a combination thereof; And

(Iii) extruding the composition into strips, profiles, films or sheets, powders, or a plurality of beads, flakes, granules or pellets.

In any of the methods according to the invention, the method comprises the steps of remelting the powder or a plurality of beads, flakes, granules or pellets, and the remelting of the strip, profile, film, sheet or molded three-dimensional geological article It may further comprise the step of extruding, molding or forming.

In one embodiment, the filler (c) is provided into the extruder together with (a) and (b) from the same aperture or hopper or as a pre-blend.

In any of the methods according to the present invention, the method may produce or form a geotechnical article in any form of CCS, geomembrane or geogrid, or an extruded or molded profile or article.

According to one embodiment of the invention, there is provided a method for forming a geological article comprising at least one layer, the at least one layer comprising: a coefficient of thermal expansion of less than about 150 ppm / ° C. at ambient temperature; Resistance to acidic media larger than polyamide 6 resin and / or resistance to basic media larger than PET resin; Resistance to hydrocarbons greater than HDPE; Creep coefficient of at least 400 MPa according to ISO 899-1 at 25 ° C., 20% yield stress and 60 min load time; And at 25 ° C., have a 1 percent secant deflection coefficient of at least 700 MPa according to ASTM D790; The at least one layer is as described herein:

(a) about 1 to about 94.5 weight percent of at least one functional group-containing polymer or oligomer;

(b) from 5 to about 98.5 weight percent of the at least one engineering thermoplastic;

(c) from about 0.5 to about 94 weight percent of at least one filler; And

(d) optionally, formed into a composition comprising up to about 93.5 weight percent of an unmodified polyolefin, ethylene copolymer or ethylene terpolymer; The method is:

(Iii) providing a polyolefin, ethylene copolymer, ethylene terpolymer or any combination thereof;

(Ii) melt kneading the polyolefin, ethylene copolymer, ethylene terpolymer or any combination thereof in the presence of free radicals with an unsaturated monomer comprising at least one reactor per molecule to thereby (a) the at least one functional group containing polymer Or forming an oligomer, wherein the reactor is carboxyl, anhydride, oxirane, amino, amido, ester, oxazoline, isocyanate or any combination thereof;

(Iii) combining the (a) functional group-containing polymer or oligomer with (b) the at least one engineering thermoplastic;

(Iii) melt kneading the combined (a) and (b);

(Iii) adding at least one filler (c) and melt kneading the combined (a), (b) and (c);

(Iii) optionally adding at least one unmodified polyolefin, ethylene copolymer or ethylene terpolymer of (d) to any of (a), (b) or (c) or a combination thereof; And

(Iii) extruding the composition into strips, films or sheets, powders, profiles, or a plurality of beads, flakes, granules or pellets.

In any of the processes according to this embodiment of the invention, (iii) and (ii) may be carried out in a first extruder, wherein (iii), (iii), (iii), (iii) and (iii) (If present) can be carried out in a second extruder.

In any method according to this embodiment of the invention, (i)-(i) and (i) (if present) may be performed in sequence in the same extruder.

In one embodiment, the polymer comprising the functional group is provided in a first zone of an extruder and the ET is provided in a molten form in powder, flake or polymer comprising the molten functional group in a second zone of the same extruder. . In another embodiment, the polymer comprising the functional group is provided in a first zone of an extruder and the ET is provided by a side extruder coupled with the first extruder in molten form to the polymer comprising the molten functional group. . The mixture of the two melts is melt kneaded in the second zone or third extruder of one of the two extruders.

In any embodiment of the present invention, the filler may be omitted. Thus, any of the compositions described above can be formed without the use of added fillers, and any of the methods described above can be performed without addition of fillers. In one embodiment, the nano-sized material is not considered to constitute a filler.

In one embodiment of the invention, the compatibilized blend provides improved weldability to non-compatibilized HDPE or MDPE molded or extruded articles, especially strips formed from articles, in particular strips from the compatibilized blend, compared to strips of the same dimensions. do. The improved weldability exhibits rapid weld formation and / or high final weld strength and / or welding ability to maintain its properties under prolonged loads. The improved weld strength is significantly better compared to HDPE and MDPE at temperatures above 45 ° C. The improved weldability is provided when the article, in particular the strip, comprises a compatibilized blend filled with the filler according to the invention.

In one embodiment, the improved weldability of the commercial blend is particularly evident when the welding is ultrasonic welding. Due to the effect of the commercial blend, strips or other articles formed from the commercial blend provide very strong bonds between the welded portions. The bond strengths obtained when the articles formed from the commercial blends of the present invention are welded to each other are stronger than the bonds obtained from similar prior art articles except those made from HDPE or MDPE.

Thus, the present invention provides improved creep resistance at temperatures ranging from -70 ° C. to 90 ° C., greater strength and stiffness, lower CTE and a lower tendency to lose stiffness at elevated temperatures, modification of the freezing process of GRM. Higher resistance to oil, better resistance to swelling by oils and hydrocarbons, better resistance to acids and bases, UV in a wide spectrum of climatic ranges from dry to polar regions for a period of about 2 to about 100 years It is characterized by greater resistance to photo-induced decomposition and pyrolysis, and improved properties such as one or more of improved weld strength and long-term load bearing, and has a long history of providing improved polymer compositions over HDPE and MDPE. Solve the need. The compatibilizing polymer compositions of the present invention are highly preferred as CCS for high efficiency applications and CCS for GRM enhancement comprising oils, acids and bases, irritating chemicals, solvents and fuels, and thus exhibit significant improvements over the prior art.

details

Physical properties referred to herein are measured at ambient temperature, ie from about 20 ° C. to about 25 ° C., unless otherwise noted.

The following detailed description of the invention is provided in conjunction with the drawings and claims in order to enable those skilled in the art to make and use the invention and to describe the best mode contemplated by the inventor for carrying out the invention. However, it will be apparent to those skilled in the art that various modifications will exist, since the general theory of the invention has been specifically defined to provide strips that can be formed into compositions, molded or extruded articles, in particular CCS, which are particularly suitable for geological applications. . In one embodiment, the article according to the invention has improved creep resistance at temperatures in the range of −70 ° C. to + 90 ° C., and has a 1 percent secant warpage coefficient according to ASTM D790 of at least 700 MPa. In one embodiment, the article or layer used to form the article has one or more coefficients of thermal expansion less than about 150 ppm / ° C. at ambient temperature; Resistance to acidic media is greater than polyamide 6 resin, and / or resistance to basic media is greater than PET resin; Resistance to hydrocarbons is greater than HDPE; According to ISO 899-1, a creep coefficient of at least 400 MPa at 25 ° C. with a load of yield stress of 20% and a load time of 60 minutes; According to ASTM D790, the 1 percent secant deflection coefficient at 25 ° C. is at least 700 MPa.

Blends, molded or extruded articles and especially strips or CCSs formed from strips typically comprise at least one layer, which layer (a) contains at least one functional group containing polymer or oligomer comprising on average at least one functional group per molecule From about 1 to about 94.5 weight percent of composition wherein the at least one functional group is selected from carboxyl, anhydride, oxirane, amino, amido, ester, oxazoline, isocyanate or any combination thereof; (b) at least one engineering thermoplastic material that is about 5 to about 98.5 weight percent of the composition; (c) from about 0.5 to about 94 weight percent of at least one filler; And (d) optionally up to about 93.5 weight percent of an unmodified polyolefin, ethylene copolymer or ethylene terpolymer. In one embodiment, the filler (c) may be omitted, so the filler is optional in this embodiment. In an embodiment in which the filler is optional, the composition comprises (a) from about 1 to about 95 weight percent of at least one functional group-containing polymer or oligomer comprising an average of at least one functional group per molecule, wherein the at least one functional group Carboxylic, anhydride, oxirane, amino, amido, ester, oxazoline, isocyanate or any combination thereof); (b) a composition of about 5 to about 99 weight percent of at least one engineering thermoplastic; (c) optionally, up to about 94 weight percent of at least one filler; And (d) optionally, up to 94 weight percent of unmodified polyolefin.

In one embodiment, the new commercialized polymer composition is characterized by a creep coefficient of at least 400 MPa at 25 ° C. with a load of yield stress of 20% and a load time of 60 minutes, according to ISO 899-1. Most polyolefins have smaller creep coefficients than the values disclosed herein for the geotechnical articles of the present invention and are therefore generally subjected to plastic deformation mode, especially under high loads and temperature combinations above 40 ° C. Can cause premature CCS failure.

In another embodiment, the new commercialized polymer composition is characterized in that the tear strength according to ASTM D1004 is at least about 30 Newtons (N) for 1 mm thick films.

Most engineering thermoplastics do not have sufficient tear and puncture resistance, which can cause catastrophic failure of the CCS formed by such materials.

In addition, alloys of PO and ET are brittle and their tear resistance is insufficient for geotechnical applications. Surprisingly, when a balanced composition of PO incorporating a relatively large amount of relatively elastic polyolefin in the form of a compatibilizer defined herein is introduced into a blend (alloy) of PO and ET, the tear strength is improved to provide a geological application to the composition. This becomes possible.

As used herein, the term “compatibility agent” refers to a functional group-containing polymer or oligomer, such as a copolymer or terpolymer comprising on average at least one reactive group per chain, or contains a functional group and is grafted by a functional group By modified polyolefin or ethylene copolymer or ethylene terpolymer which is functionalized by functional groups and / or comprises on average at least one reactive group per chain. Thus, the compatibilizer comprises at least one functional group per chain (ie polymer or oligomer modified by at least one reactive group on average per chain).

The term "functional group-containing polymer or oligomer" herein refers to copolymers or oligomers containing "mer" units derived from functional group-containing monomers, or polymers functionalized by grafting a functional group-containing moiety to a chain or backbone of the polymer, for example. , Either copolymer or oligomer. In both cases, the functional group may be one or more of carboxyl, anhydride, oxirane, amino, amido, ester, oxazoline, isocyanate or combinations thereof. The term "functionalized" or "functional group containing" means any product in which a reactive group is covalently bonded to a polymer or oligomer chain. As described herein, the functional group is introduced by grafting onto a polymer or oligomer already formed, or the functional group-containing monomer is converted into a chain or backbone of the polymer or oligomer by copolymerization of one or more non-functional group-containing monomers with one or more functional group-containing monomers. It can be introduced by forming a copolymer or terpolymer included in.

As used herein, the term "self compatibilizer" refers to a modified polymer (compatibilizer) derived from an unmodified polyolefin or ethylene copolymer or ethylene terpolymer, wherein the unmodified polymer is defined by a functional group containing reactant. Grafted or functionalized, the grafting and functionalization being immediately prior to the melt kneading of the self compatibilizing agent and optionally any unmodified polyolefin or ethylene copolymer or ethylene terpolymer with the engineering thermoplastic component. Happens in situ The functional group may be a group that is reactive with a component of the engineering thermoplastic component. The term “in situ” means that the molten self compatibilizer and the engineering thermoplastic component are mixed immediately after preparation without having a cooling step between the steps.

As used herein, the term “external compatibilizer” is obtained by grafting a commercially available or functional group containing reactant to a suitable unmodified polyolefin or ethylene copolymer or ethylene terpolymer, the graft being an engineering thermoplastic and an optional This occurs before the point of introduction of the compatibilizer into the blend comprising the polyolefin or ethylene copolymer or ethylene terpolymer which is not modified. The external compatibilizer is provided as a solid pellet or powder or flake or any other form with a solid engineering thermoplastic and optionally a solid unmodified polyolefin or ethylene copolymer or ethylene terpolymer, the mixture being melted and then melt kneaded. do.

In one embodiment, the composition according to the invention comprises the steps of introducing an unmodified polymer, an unsaturated functional group containing reactant and a free radical initiator into the extruder; First melt kneading these materials to cause the reactants to react with the polymer to graf the reactive groups onto the polymer chain to form a self-compatibility agent; Introducing a melt engineering thermoplastic into the extruder; Melt kneading downstream of the self compatibilizing agent and engineering thermoplastic in the extruder or the second extruder; Optionally adding a separate unmodified polymer after the first melt kneading and before or after the introduction of the engineering thermoplastic material and further melt kneading thereafter; And extruding the composition through a die to form strips, profiles, three-dimensional articles, films or sheets, powders or a plurality of beads, flakes, granules or pellets.

In any embodiment in which an unmodified polyolefin, ethylene copolymer or ethylene terpolymer (PO) phase is present, the PO is hydrolytic stability (especially in acids and bases that attack ET). To tear and puncture resistance, providing these advantages over a wide temperature range, especially at temperatures below 0 ° C., and high melt strength, which is an important parameter in extrusion and blow molding.

The engineering thermoplastic (ET) phase has improved barrier properties for stiffness, strength, dimensional stability, creep resistance at temperatures higher than about 40 ° C., resistance to oils and fuels, and diffusion of other materials through molded or extruded articles. , Improved coefficient of friction (important for welding and friction with GRM), lower coefficient of thermal expansion (CTE) than PO, and high to enable slow diffusion of harmful compounds through polymer articles and slow extraction and evaporation of HALS and UV absorbers Provided is a composition having barrier properties.

Unless otherwise specified, the properties of the polymers described below are measured at ambient temperature, ie from about 20 ° C. to about 25 ° C. and atmospheric pressure conditions.

In one embodiment of the invention, it is suitable for geotechnical applications including CCS, geogrid, geomembrane and soil reinforcement, and has high creep resistance, ultraviolet (at temperatures ranging from -70 ° C to + 90 ° C). UV) Provides a commercially available polymer composition characterized by high resistance to light and heat induced degradation and stiffness suitable for applications where the 1% secant warpage coefficient according to ASTM D790 measured at ambient temperature is at least 700 MPa. In one embodiment the commercialized polymer composition of the present invention has a percent percent secant modulus according to ASTM D790 of at least 600 MPa when measured at 45 ° C., and in another embodiment, the commercialized polymer composition of the present invention is measured at 70 ° C. The 1 percent secant modulus according to ASTM D790 is at least 500 MPa. In one embodiment the polymer composition has a one percent secant deflection coefficient according to ASTM D790 at least 10% greater than HDPE when measured at about 45 ° C., and in another embodiment the polymer composition has been measured at about 70 ° C. The 1 percent secant warpage coefficient according to ASTM D790 is at least 10% better than HDPE. In one embodiment the compatibilizing polymer composition has a 1% secant warpage coefficient according to ASTM D790 at least 25% greater than HDPE when measured at about 45 ° C., and in other embodiments the polymer composition has been measured at about 70 ° C. At least 25% better secant warpage coefficient according to ASTM D790 than HDPE.

In one embodiment, the present invention provides a geotechnical article comprising at least one layer, the at least one layer having one or more thermal expansion coefficients of less than about 150 ppm / ° C at ambient temperature; Resistance to acidic media is greater than polyamide 6 resin, and / or resistance to basic media is greater than PET resin; Resistance to hydrocarbons is greater than HDPE; According to ISO 899-1, a creep coefficient of at least 400 MPa at 25 ° C. with a load of yield stress of 20% and a load time of 60 minutes; According to ASTM D790, it has a property that a 1 percent secant deflection coefficient at 25 ° C. is at least 700 MPa.

In one embodiment, the at least one layer comprises (a) from about 1 to about 94.5 weight percent of at least one functional group-containing polymer or oligomer comprising an average of at least one functional group per molecule, wherein the at least one functional group Carboxyl, anhydride, oxirane, amino, amido, ester, oxazoline, isocyanate or any combination thereof); (b) from about 5 to about 98.5 weight percent of at least one engineering thermoplastic; (c) from about 0.5 to about 94 weight percent of at least one filler; And (d) optionally, up to 93.5% by weight of an unmodified polyolefin, ethylene copolymer or ethylene terpolymer.

In another embodiment, the at least one layer comprises (a) from about 1 to about 95 weight percent of at least one functional group-containing polymer or oligomer comprising on average at least one functional group per molecule, wherein the at least one functional group Carboxylic, anhydride, oxirane, amino, amido, ester, oxazoline, isocyanate or any combination thereof); (b) a composition of about 5 to about 99 weight percent of at least one engineering thermoplastic; (c) optionally up to about 94 weight percent of at least one filler; And (d) about 94% by weight of an optionally unmodified polyolefin. In one embodiment, the content of (b) is from about 90% to about 10% by weight. In one embodiment, the at least one engineering thermoplastic material is (i) polyamide; (Ii) polyester; (Iii) polyurethane; Or (iii), (ii) and (iii) two or more copolymers, block copolymers, blends or combinations.

In one embodiment, when present, the filler is in powder, whisker, or fiber form, and in one embodiment, when in powder form, the average particle size is less than about 30 microns. In one embodiment, the filler is metal oxide, metal carbonate, metal sulfate, metal phosphate, metal silicate, metal borate, metal hydroxide, silica, silicate, aluminate, alumino-silicate, chalk, talc, dolomite , Organic or inorganic fibers or whiskers, metals, metal-coated inorganic particles, clay, kaolin, industrial ash, concrete powder, cement, dolomite, wollastonite or mixtures of two or more thereof.

In one embodiment, the functional group containing polymer or oligomer is a modified polyolefin, ethylene copolymer or ethylene terpolymer and the functional group is grafted to the polymer or oligomer. It may be formed in situ, or may be formed by functionalizing PO prior to melt kneading with ET (in this case, a self compatibilizer), or as an additive, for example with ET and any unfunctionalized PO. May be added to the extruder (in this case an external compatibilizer).

In one embodiment, the functional group-containing polymer or oligomer is a copolymer or terpolymer of (1) at least one unsaturated monomer and (2) at least one functional group-containing unsaturated monomer, wherein the functional group-containing unsaturated monomer is at least one unsaturated Group and at least one functional group. Such copolymers or terpolymers are external compatibilizers. Some specific examples of functional group-containing polymers or oligomers include polyethylene grafted with maleic anhydride, ethylene-acrylic acid or methacrylic ester copolymers or terpolymers grafted with maleic anhydride, maleic anhydride Propylene homopolymer or copolymer, ethylene-alpha olefin polymer grafted with maleic anhydride, ethylene-propylene rubber, glycidyl methacrylate or acrylate (GMA) grafted with maleic anhydride Polyethylene, GMA-grafted ethylene-acrylic acid or methacrylic esters, copolymers or terpolymers, GMA-grafted propylene homopolymers or copolymers, GMA-grafted ethylene-alpha olefin polymers, GMA-grafted ethylene-propylene rubbers , Acrylic acid or meta Ethylene copolymer or terpolymer grafted with lylic acid, acrylic acid and methacrylic acid ionomer, styrene-maleic anhydride copolymer or terpolymer, styrene-acrylic acid or styrene-methacrylic acid copolymer or terpolymer, ethylene-glycid Copolymers or terpolymers of dill methacrylate or ethylene-glycidyl acrylate, or any combination thereof.

In one embodiment, (d) the ethylene copolymer or ethylene terpolymer, when present in an unmodified polyolefin, is independently polyethylene, ethylene-vinyl acetate, polypropylene, ethylene-alpha olefin elastomer, ethylene-propylene elastomer, ethylene -Propylene diene elastomer, ethylene-acrylate ester or methacrylate ester copolymer or terpolymer, or any copolymer or combination thereof.

In one embodiment, the sensitivity to hydrolysis by acid or base may not be solved simply by commercialization. In one embodiment, the diffusion of such harmful compounds into the polymer blend is reduced and the hydrolysis resistance is enhanced by blocking of the hydrophilic end groups or side groups of the molecules in the blend—particularly in the ET phase. These are novel aspects of embodiments of the invention disclosed in this application.

The unmodified PO phase is in particular polyethylene, ethylene-vinyl acetate, polypropylene homopolymers and copolymers, ethylene-alpha olefin elastomers, ethylene-propylene elastomers, ethylene-propylene diene elastomers, ethylene-acrylate esters or methacrylate ester copolymers. And non-limiting methods from the group comprising polymers and terpolymers, and combinations thereof.

Representative POs according to the invention are commercially available products such as polyethylene, such as Attane ™ and Dowlex ™ from DOW, Petrothene ™ from Equistar, Sabic ™ from Sabic, Marlex ™ from Chevron-Phillips and Exceed ™ from ExxonMobil; Ethylene-alpha olefin elastomers such as commercially available products such as Engage ™ from DOW, Exact ™ from ExxonMobil and Tafmer ™ and Evolue ™ from Mitsui; Or commercially available products such as ethylene-propylene elastomers or ethylene-propylene diene elastomers such as Vistalon ™ from ExxonMobil and Nordel ™ from DOW; Commercially available products such as ethylene-acrylate ester or methacrylate ester copolymers and terpolymers such as Elvaloy ™ from Dupont and Lotryl ™ from Arkema; Butyl rubber, nitrite rubber, silicone elastomer, polyurethane elastomer, styrene block copolymer; Commercially available products such as, for example, Kraton ™ by Kraton et al., And the like.

Representative ET phases can in particular be selected in a non-limiting manner from polyamides, polyesters, polyurethanes, polyester block amides or any combination thereof. In one embodiment, the polyamide is in particular a commercially available product such as polyamide 6, for example Ultramid ™ from BASF, Grilon ™ from EMS-Grivory and Akulon ™ from DSM; Polyamide 66, such as commercially available products such as Ultramid ™ from BASF, Polynil ™ from Nilit, Grilon ™ from EMS-Grivory and Akulon ™ from DSM; Commercially available products such as polyamide 6-66 copolymer, polyamide 6T, polyamide 6-12, polyamide 11 and polyamide 12, for example Rilsan ™ from Arkema; Polyamide 46, for example a commercially available product such as Stanyl ™ from DSM; And aliphatic polyamides selected in a non-limiting manner from the group comprising polyether block amides (PEBA), copolymers and blends thereof. One important source of cost effective polyamides for the commercial blends according to the present invention is recycled polyamide fibers from the textile industry.

In one embodiment, the polyesters in the present invention are aromatic, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), copolyesters, copolymers and blends thereof Diacid-glycol esters. Commercially available products are Eastapak ™ and Eastar ™ from Eastman, and Ultradur ™ from BASF. Two important sources of cost effective polyesters for the commercial blends according to the invention are ( i ) generally regrind recycled PET beverage bottles, ( ii ) recycled fibers from the textile industry.

In one embodiment, the polyurethanes in the present invention are aliphatic and / or aromatic thermoplastic polyester-urethanes, polyether-urethanes, copolymers and blends thereof. Aliphatic polyurethanes may be more desirable because of their good resistance to degradation induced by UV light and heat. Suitable commercially available polyurethanes in the present invention are Pellethane ™ from DOW, Estane ™ and Tecothane ™ from Noveon, and Desmopan ™ from Bayer.

The term “commercialization” hereafter refers to a stable dispersion of one polymer in another, where the two polymers do not mix with each other due to limited compatibility in the solidified state such that crystallization and in the absence of the commercialization described herein There is a tendency to phase-separate upon solidification.

The term "stable dispersion" means that the interface between the dispersed phase and the continuous phase comprises stabilizer molecules or macromolecules and differs from the two aforementioned phases (PO and ET), and is compatible with both PO and ET. It means dispersion when there is. Either ET or PO may constitute a continuous phase depending on the relative concentrations in the composition. The dispersion is characterized by very limited phase-separation upon crystallization and solidification. Typical morphology associated with stable dispersion is a very fine small nodule or lamella of the first polymer in the continuous phase of the second polymer. Such small nodules or thin plates generally have a diameter or size of about 30 microns or less, in one embodiment about 10 microns or less in diameter or size, and in other embodiments about 5 microns or less in diameter or size. And in one embodiment about 3 microns or less and in one embodiment about 1 micron or less. In one embodiment, the composition comprises a continuous phase and a discontinuous phase dispersed throughout the continuous phase, with substantially all of the regions having a largest dimension of about 10 microns or less. In one embodiment, substantially all of the domains have a largest dimension of about 3 microns or less.

The stable dispersion retains its structure and properties in one or more of melting, extrusion, molding, forming, welding and service without phase separation and deterioration of physical and chemical properties. In one embodiment, at least one phase (dispersed or continuous phase) is provided in covalent linkage with a compatibilizer.

In one embodiment, the functional group-containing copolymer or oligomer is selected in a non-limiting manner from ( i ) modified polymers and ( ii ) copolymers and terpolymers. Modified polymers having pendant functional groups and / or terminal functional groups may be selected in a non-limiting manner from carboxyl, anhydride, oxirane, amino, ester, oxazoline, isocyanate and any two or more combinations thereof, for example For example, maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-acrylic acid ester copolymer or terpolymer, maleic anhydride grafted propylene homopolymer and copolymer, maleic anhydride Grafted ethylene-alpha olefin polymer, ethylene-propylene rubber grafted with maleic anhydride, polyethylene grafted with glycidyl methacrylate or acrylate (GMA), ethylene-acrylic acid ester copolymer or grafted with GMA Propylene Homo Grafted with Polymer, GMA Polymers and copolymers, ethylene-alpha olefin polymers grafted with GMA, ethylene-propylene rubbers grafted with GMA, ethylene copolymers and terpolymers grafted with acrylic acid or methacrylic acid, acrylic acid and methacrylic acid ionomers and combinations thereof.

Examples of commercially available functionalized polymers applied to commercialize blends as external compatibilizers according to the present invention include Artama's Lotader ™, Polyram's Bondyram ™, Crompton's Polybond ™, Equistar's Integrate ™, DSM's Yparex ™, DOW Primacor ™ and Amplify ™, Eastman's Epolene ™, ExxonMobil's Escor ™, Optema ™ and Exxelor ™, Dupont's Fusabond ™, Bynel ™, Elvaloy ™ and Surlyn ™, Honeywell's AC ™ modified polyolefin, Mitsubishi's Modic-AP ™ , Mitsui's Admer ™, NOF's Modiper ™ and Sumitomo's lgetabond ™.

In one embodiment, the functional and reactive group-containing copolymers and terpolymers used as external compatibilizers are copolymers and terpolymers of at least one unsaturated monomer and at least one functional unsaturated monomer, wherein the functional unsaturated monomer is at least One unsaturated group and at least one functional group selected in a non-limiting manner from carboxyl, anhydride, oxirane, amino, ester, oxazoline, isocyanate and combinations thereof. For example, the copolymer may be styrene maleic anhydride copolymer and terpolymer, such as Sartomer's SMA ™ resin, UMG's UMG AXS ™, UCB's Synthacryl ™, and the like.

According to one embodiment, the compatibilizer provides good compatibility between the PO and ET phases, at which the two phases act at these interfaces to mix, encapsulate the dispersed phase, and block the polar groups on the ET phase. This is due to the lower enthalpy.

According to one embodiment of the invention, the compatible blends as defined above are provided by melt kneading a ET and PO phase and a compatibilizer selected from one or more external compatibilizers, self compatibilizers or mixtures thereof.

According to another embodiment, the functional group is reactive with at least one end group or side group of the engineering thermoplastic in the molten state. In particular, the end groups and / or side groups of the ET are selected in a non-limiting manner from one or more amino, hydroxyl or carboxyl groups or combinations thereof.

In one embodiment, the reaction occurs between an anhydride or oxirane group of a compatibilizer having amino, amido, hydroxyl or carboxyl end groups or side groups of the engineering thermoplastic.

In another embodiment, the external compatibilizer between the PO and ET phases is by means of solution polymerization in the reactor or melt kneading in a reactive extruder, thereby modifying the at least one polymer by at least one functional group. Is provided.

The term "reactive extruder" means an extruder in which the polymer or oligomer is functionalized by the reactive group by reaction between the reactive group containing compound and the molten polymer, wherein at least one part of the reaction takes place in the extruder. In one embodiment, the present reaction grafts functional groups onto the polymer or oligomer backbone or backbone.

According to another embodiment, the compatibilizer between the PO phase and the ET phase comprises solution polymerization of the PO, an unsaturated monomer comprising at least one reactive group and a free radical source in a reactor or melt kneading in an extruder, Provided by modifying at least one portion on the PO by at least one functional group.

According to another embodiment, the external compatibilizer is in particular polyethylene, ethylene-vinyl acetate, polypropylene, propylene copolymers and terpolymers, ethylene-alpha olefin elastomers, ethylene-propylene elastomers, ethylene-propylene diene elastomers, ethylene-acrylates. Provided by modifying a polymer selected in a non-limiting manner from the group comprising ester or methacrylate ester copolymers and terpolymers, butyl rubbers, nitrite rubbers, silicone elastomers, polyurethane elastomers or any combination thereof.

According to another embodiment, the aforementioned polymers can be selected from (1) PO polymers in an extruder; (2) at least one unsaturated monomer comprising at least one reactive group per molecule; And (3) optionally at least one free radical initiator by melt kneading, wherein the extruder is in one embodiment a multi screw extruder and in another embodiment a twin screw extruder.

In one embodiment, a polyolefin, ethylene copolymer, ethylene terpolymer or any combination thereof is provided, followed by melt kneading with an unsaturated monomer comprising at least one reactive group per molecule in the presence of a free radical to form at least one functional group. Containing polymers or oligomers (a), wherein the reactive groups include, for example, carboxyl, anhydride, oxirane, amino, amido, ester, oxazoline, isocyanate or combinations thereof. The functional group-containing polymer or oligomer formed is then combined with at least one engineering thermoplastic material and the combination is melt kneaded.

The melt kneading is optionally provided in a multi-screw extruder, in particular a twin screw extruder, at a temperature in the range from about 130 ° C to about 300 ° C.

According to another embodiment, the polymer described above is modified by melt kneading in an extruder, wherein the at least one unsaturated monomer comprises at least one reactive group per molecule, maleic anhydride, acrylic acid, methacrylic acid , Glycidyl acrylate or methacrylate (GMA) or combinations thereof.

E.g,

(Iii) DOW's Attane ™ and Dowlex ™, Equistar's Petrothene ™, Sabic's Sabic ™, Chevron-Phillips' Marlex ™ and ExxonMobil's Exceed ™, DOW's ethylene-alpha olefin elastomer Engage ™, ExxonMobil's Exact ™ And Tafmer ™ and Evolue ™ from Mitsui; Ethylene-propylene elastomers or ethylene-propylene diene elastomers from ExxonMobil Vistalon ™ and Nordel ™ from DOW; Ethylene-acrylate or methacrylate ester copolymers and terpolymers from Dupont Elvaloy ™ and Lotryl ™ from Arkema; PO polymers selected from butyl rubber, nitrite rubber, silicone elastomers, polyurethane elastomers, commercially available products of Kraton's styrene block copolymer Kraton ™, and the like,

(Ii) free radical initiators and optionally in an extruder with unsaturated reactive group containing monomers selected from, for example, maleic anhydride or acrylic acid or methacrylic acid or glycidyl methacrylate or glycidyl acrylate Modified by melt kneading in the presence of a vinyl monomer, the extruder is in one embodiment a multi screw extruder and in another embodiment a twin screw extruder. As used herein, the term "multi screw extruder" is defined to include any extruder having two or more screws.

According to another embodiment, the compatibilizer used for the compatible blend is polyethylene grafted with maleic anhydride, ethylene-acrylic acid ester copolymer or terpolymer grafted with maleic anhydride, maleic anhydride Grafted propylene homopolymer or copolymer, ethylene-alpha olefin polymer grafted maleic anhydride, ethylene-propylene rubber grafted maleic anhydride, glycidyl methacrylate or acrylate (GMA) Grafted polyethylene, ethylene-acrylic acid ester copolymer or terpolymer grafted GMA, propylene homopolymer or copolymer grafted GMA, ethylene-alpha olefin polymer grafted GMA, ethylene-propylene rubber grafted GMA, acrylic acid or meta Ethyl grafted Copolymers and terpolymers, restricted from acrylic acid and methacrylic acid ionomer, and mixtures thereof are selected without.

For example, the appropriate, commercially functional polymers usable in to commercialize the blend as an external compatibilizer according to the present invention, Arkema's Lotader ^TM, Polyram company Bondyram ^TM, Crompton Corporation Polybond ^TM, Equistar Corporation Intergrate ^TM, DSM's Yparex ^TM , DOW's Primacor ^TM and Amplify ^TM , Eastman's Epolene ^TM , ExxonMobile's Escor ^TM , Optema ^TM and Exxelor ^TM , Dupont's Fusabond ^TM , Bynel ^TM , Elvaloy ^TM and Surlyn ^TM , Honeywell's AC ^TM modified polyolefin, Mitsubishi's Modic AP ^TM , Admer ^{TM from} Mitsui, Modiper ^{TM from} NOF, and lgetabond ^{TM from} Sumitomo.

According to another embodiment, the aforementioned external compatibilizer comprises at least one copolymer or terpolymer of (1) at least one unsaturated monomer, and (2) an unsaturated monomer containing at least one functional group. For example, (1) unsaturated monomers may include ethylene, alpha olefins, styrene, acrylic acid or methacrylic acid esters or amides, vinyl esters or polyenes, and (2) unsaturated monomers containing functional groups may be acrylic acid, methacrylic Acids, maleic anhydride or GMA, or other similar unsaturated monomer groups and functional groups.

According to another embodiment, the functional group of an unsaturated monomer containing at least one functional group can be selected without limitation from the group consisting of carboxyl groups, anhydrides, oxiranes, amino, esters, oxazoline and isocyanate groups or combinations thereof. have.

According to another embodiment, the polymer or oligomer containing functional groups is prepared by a polymerization process carried in one of gaseous, dissolved phase, solution, emulsion or dispersion.

According to another embodiment, the polymer or oligomer containing the functional group is a styrene maleic anhydride copolymer or terminator, such as SMATM commercially available resin, SMA ^™ from UMG, UMG AXS ^{™ from} UMG, Syntharyl ^{™ from} UCB resin, or the like. It is selected without limitation from the polymer.

According to one embodiment of the invention, the composition is rich in PO in the continuous phase and rich in ET in the dispersion phase. Commercialized polymer compositions are characterized by higher resistance to hydrolysis compared to polyimide 66 and PET. The geotechnical article comprising the polymer composition of the present invention has at least one improved hydrolysis resistance and / or tear strength compared to polyester or polyamide based products, improved stiffness, strength and creep resistance compared to HDPE, Improved chemical resistance compared to hydrocarbon fuels, in particular, provides improved coefficient of friction, improved weldability and lower CTE compared to polyethylene, especially HDPE, when the composition is exposed to temperatures above 40 ° C.

According to one embodiment of the invention, the composition is rich in ET in the continuous phase and rich in PO in the dispersion phase. In this embodiment, the commercialized polymer composition has a higher resistance to creep, higher stiffness, higher strength, higher tear resistance, stronger weldability, improved coefficient of friction with GRM compared to polyethylene, especially HDPE, It is characterized by having lower CTE, lower diffusion rates of HALS and UV absorbers from polymeric compounds and hazardous compounds through polymeric articles and improved resistance to expansion of oils and fuels. In one embodiment, geotechnical articles, in particular geomembranes, reinforcing strips and shaped articles comprising said commercialized polymer compositions and CCS, in particular compared to HDPE-based products, have improved dimensions, especially at temperatures above 40 ° C. Provides safety and creep resistance.

In one embodiment, the polymer composition comprises (a) about 1 to about 94.5% by weight of at least one functional group-containing polymer or oligomer comprising, on average, at least one functional group per molecule, wherein the at least one functional group is a carboxyl group, Anhydride, oxirane, amino, amido, ester, oxazoline and isocyanate or combinations thereof), (b) at least one engineering thermoplastic composition of about 5 to about 98.5 weight percent, (c) at least From about 0.5 to about 94 weight percent of one filler, and (d) optionally up to about 93.5 weight percent of an unmodified polyolefin, ethylene copolymer or ethylene terpolymer.

In another embodiment, the polymer composition comprises (a) 1 to 95% by weight of at least one functional group-containing polymer or oligomer comprising, on average, at least one functional group per molecule, wherein the at least one functional group is a carboxyl group, anhydride Ride, oxirane, amino, amido, ester, oxazoline and isocyanate or combinations thereof), (b) composition of about 5 to about 99 weight percent of at least one engineering thermoplastic, (c) optionally Up to about 94 weight percent of at least one filler, and (d) optionally up to about 94 weight percent of unmodified polyolefin.

According to another embodiment, the polymer composition is provided by melt kneading in an extruder, and in one embodiment, (i) from 10 to 90% by weight of ET in a multi screw extruder at about 130 ° C. to 320 ° C., (ii ) From about 10 to about 90% by weight of PO and / or self-compensating agent, and (iii) from 0 to about 30% by weight of external compatibilizer. The percentage contents mentioned herein refer to percentages based on the total weight of the composition, unless stated otherwise.

In one embodiment, the polymer composition is provided melt melt kneaded in an extruder, and in one embodiment, (i) about 10 to about 90 weight percent of the polymer composition in a multi-screw extruder at a temperature ranging from about 130 ° C to 320 ° C. Polyethylene terephthalate (PET), or polyamide 6 or polyamide 66, (ii) from 10 to 90% by weight of polyethylene, ethylene copolymers, ethylene terpolymers, or ethylene-alpha olefin elastomers and optionally their self compatibilizers, And (iii) from 0 to about 30% by weight of external compatibilizer, maleic anhydride or GMA modified polyethylene or propylene or ethylene copolymer or ethylene terpolymer, or a mixture comprising ethylene-alpha olefin.

According to another embodiment, the polymer composition is provided by melt kneading in an extruder, and in one embodiment, (i) from 10 to 90% by weight in a multi screw extruder at a temperature in the range from about 130 ° C. to about 320 ° C. ET, (ii) in a mixture comprising about 10 to 90 weight percent PO. At least 1% by weight of the PO, in particular at least about 5% and preferably at least 20% by weight of PO, is functionalized and the functionalized part is a self compatibilizer.

According to another embodiment, PO is functionalized with an anhydride, carboxyl or oxirane group to form a self-compatibility agent.

According to yet another embodiment, the aforementioned compositions are provided by melt kneading in an extruder, and in one embodiment, (i) about 5 to about 90 weight in a multi screw extruder at a temperature ranging from about 130 ° C. to about 320 ° C. % Of ET, (ii) 0 to about 90 weight percent PO, and (iii) about 0.5 to about 95 weight percent functionalized PO. The functionalized PO is then functionalized in the first extruder prior to mixing ET and PO in the second extruder, or functionalized in the first part of the same extruder used to mix EO and PO using the functionalized PO. According to another embodiment, functionalization of PO comprises at least one unsaturated monomer wherein at least a portion of PO comprises (i) at least one reactor per molecule, (ii) free radical initiator, and (iii) optionally in an extruder. And melt kneaded with a second unsaturated monomer, oil, wax and / or heat stabilizer. The functionalization process is one embodiment provided in a multi screw extruder, in particular in a double screw extruder, in the temperature range from about 130 to about 320 ° C.

According to another embodiment, a residence time of about 10 to 180 seconds, in a temperature range of about 130 to about 230 ° C., from 0.001 to about 3 weight percent free radical initiator, 0.01 to 5 weight percent maleic anhydride or 0.01 to PO is modified by melt kneading in an extruder in the presence of about 20% by weight of GMA and optionally 5% by weight of copolymer, in particular styrene, so that from about 0.01 to about 4% by weight maleic anhydride or from about 0.01 to 19 Weight% GMA is grafted to PO.

According to another embodiment, the polymer blend composition further comprises a filler. The fillers are in particular metal oxides, metal carbonates, metal sulfates, metal phosphates, metal silicates, metal borates, metal hydroxides, silicas, silicates, aluminates, alumino-silicates, chalk, talc, kaolin, clays, dolomites, fibers and It is selected without limitation from the group comprising whiskers, metals, metal-coated inorganic fillers, wollastonite, kaolin, industrial materials, concrete powders and cements, or mixtures thereof. In one embodiment, the filler comprises one or more of calcium carbonate, talc, clay, kaolin, industrial ash and barium sulphate.

The introduction of fillers into the blends, depending on creep resistance, scratch resistance, expansion resistance, opacity and improved thermal conductivity of oils and fuels, resistance to UV light and thermal induced decomposition, improved manufacturing capacity, lower CTE and improved Note that the weldability is increased. Improved thermal conductivity prevents heat buildup in commercially available polymer compositions when exposed to sunlight and heat, as the CCS surface is less heated by sunlight, resulting in less UV and thermally induced decomposition Slow compared to

In one embodiment, the polymer composition of the present invention comprises about 0.5% to about 70% by weight filler. In one embodiment, the polymer composition of the present invention comprises about 5% to about 50% by weight filler. In one embodiment, the polymer composition of the present invention comprises about 10% to about 40% by weight filler.

In one embodiment, if the filler comprises at least one of calcium carbonate, talc, dolomite, silica, clay, wollastonite, kaolin, industrial ash and barium sulphate, the CTE of the article made from the commercially available blends of the present invention is about 125 ppm Lower than / ° C. In one embodiment, if the filler comprises one or more of calcium carbonate, talc, dolomite, silica, clay, wollastonite, kaolin, industrial ash and barium sulphate, the CTE of the article made from the commercially available blends of the present invention is about 100 ppm / Lower than ℃. In one embodiment, if the filler comprises one or more of calcium carbonate, talc, dolomite, silica, clay, wollastonite, kaolin, industrial ash and barium sulphate, the CTE of the article made from the commercially available blends of the present invention is about 90 lower than ppm / ° C. In another embodiment, if the filler comprises one or more of calcium carbonate, talc, dolomite, silica, clay, wollastonite, kaolin, industrial ash and barium sulphate, the CTE of the article made from the commercially available blends of the present invention is about 80 ppm Lower than / ° C. As a result of improved CTE, that is, reduced CTE as compared to materials such as HDPE, makes articles made according to the invention more dimensionally stable than articles formed from conventional materials such as HDPE.

In addition to the advantages of the fillers described above, introducing fillers into commercialized polymer compositions can result in low torque results in the extruder, reduce power consumption, increase production rates, and reduce decomposition of components of the mixture. do. The impact of low extruder torque is most important when the filler is surface treated so that improved compatibility with PO and / or ET can be obtained.

According to another embodiment, the surface treated fillers, in particular ultrafine fillers and preferably nano-sized fillers, are mixed and stabilized with a dispersed commercial blend of ET and PO. Mixtures of fillers surface treated with the aforementioned compatibilizers increase compatibilization. An increase in compatibilization is provided when the dispersed phase regions (generally in the form of nodules) are spaced from each other by mineral particles, thus delaying coalescence between adjacent regions. Since the compatibilizer allows stable dispersion formation during melt kneading, the combination of filler and compatibilizer is elevated and fillers, particularly nano-size fillers, have a low tendency to fuse during cooling and crystallization.

In one embodiment, the composition further comprises nano sized particles characterized by barrier properties, except that the transmittance of the composition to molecules having a molecular weight less than about 1000 Daltons does not include the nanosize particles. At least 10% lower compared to compositions comprising the same composition. In one embodiment, the nano-sized particles are nano-clay, nano-silica, nano-silicate, nano-alumosilicate, nano-zinc oxide, nano-titanium oxide, nano-zirconium oxide, nano-talc, nano- Tubes, nano-metal particles and / or flakes, carbon black, nano size sulfides and sulfates and nano size celluloses, lignin, proteins from plant or animal and combinations of two or more thereof.

In one embodiment, the composition further comprises an additive selected to be a heat stabilizer, a hindered amine light stabilizer (HALS), an organic UV absorber, an inorganic UV absorber, a hydrolysis inhibitor, or a combination of two or more of these additives.

Accordingly, the polymer composition as defined above may comprise an effective amount of hydrolysis inhibitor additive (hereinafter abbreviated as "HIA"). Hydrolysis inhibiting additives inhibit hydrolysis of engineering thermoplastics in commercialized blends during service, particularly when the polyester is an engineering thermoplastic and the medium around the CCS is characterized by pH ≧ 7, especially pH ≧ 9. HIA is a carbodiimide, in particular a commercially available product, for example poly-carbodiimide such as Stabaxol ^{™ from} Rhein Chemie, block isocyanates, epoxy resins, phenolic resins, novolak resins, melamine resins, urea resins, glycolurils Resins, triisocyanuric acid and derivatives thereof, styrene-maleic anhydride resins, aromatic and cycloaliphatic diacids and their anhydrides can be selected in a non-limiting manner.

In one embodiment, the hydrolysis inhibitor reacts with end groups or side groups of the at least one engineering thermoplastic material, and the hydrolysis inhibitor is carbodiimide, poly-carbodiimide, block isocyanate, epoxy resin, phenol resin, At least one selected from novolak resins, melamine resins, urea resins, glycoluril resins, triisocyanuric acid and derivatives thereof, styrene-maleic anhydride resins, or aromatic or cycloaliphatic diacids and anhydrides thereof.

According to another embodiment, the method of providing the composition and strips thereof is described as providing a blend that is commercialized by melt kneading and forming a geotechnical article by molding or extrusion. The method comprises the steps selected from: (i) providing a functionalized polymer, ET and optionally PO in an extruder (in one embodiment a multi screw extruder, in another embodiment a twin screw extruder) Wherein the polymer is in the form selected without limitation from pellets, granules, flakes, powders, chips, fibers, irregular aggregates and combinations thereof, optionally the masterbatch of fillers in the polymer and the masterbatch of additives in the second polymer From (ii) melting and polymerizing the polymer by shear and heat in the first part of the extruder, (iii) melt kneading the optionally melted mixture, (iv) optionally mixing the filler, eg For example, the filler is provided in powder or aggregate by a feeder (in one embodiment a secondary feeder) through an opening in the outer barrel; The filler is wetted by the molten polymer blend and mixed to melt; Optionally through at least one gate, opening or vent of the extruder, trapped air and moisture are removed, for example where the outlet is located upstream or downstream of the auxiliary feeder port; (v) melt kneading the mixture so that the average dispersed polymer phase diameter is less than about 30 microns, in particular less than about 10 microns, preferably less than 5 microns, optionally the filler deagglomerated and dispersed the mass. And optionally, a second outlet is located in the outer barrel prior to the die to remove gaseous components from the blend; (vi) pumping the compound through the die; Pumping is then provided, for example, by an extruder screw or optionally an additional gear pump; And (Vii) extruding the compound to form strips, sheets, profiles, pellets, beads, granules, chips, plates, three-dimensional articles or powders.

In one embodiment, the present invention provides a method of forming a geotechnical article comprising at least one layer, wherein the at least one layer has one or more of the preferred physical properties described herein formed from the compositions described herein. The method comprises the steps of (i) providing (a) at least one functional group-containing polymer or oligomer and (b) at least one engineering thermoplastic; (ii) melt kneading the combined (a) and (b); (iii) optionally (c) adding at least one filler and further melt kneading the combined (a), (b) and (c) above; (iv) optionally (d) adding at least one unmodified polyolefin, ethylene copolymer or ethylene terpolymer to (a), (b), or (c) or a combination thereof; And (v) extruding the resulting composition into strips, profiles, films or sheets, powders or a plurality of beads, three-dimensional articles, plates, granules or pellets.

In one embodiment, the present invention provides a method of forming a geotechnical article comprising at least one layer, wherein the at least one layer has one or more of the preferred physical properties described herein formed from the compositions described herein. The method comprises the steps of (i) providing an unmodified polyolefin, ethylene copolymer or ethylene terpolymer or combinations thereof; (ii) melt-kneading unmodified polyolefins, ethylene copolymers or ethylene terpolymers or combinations thereof in the presence of free radicals with unsaturated monomers having at least one reactive group per molecule, thereby characterizing on average at least one functional group per chain Forming a containing polymer or oligomer, wherein the reactor is a carboxyl group, anhydride, oxirane, amino, amido, ester, oxazoline, isocyanate or combinations thereof; (iii) combining the prepared (a) functional group-containing polymer or oligomer with (b) at least one engineering thermoplastic; (iv) melt kneading the combined (a) and (b); (v) optionally (c) adding at least one filler and further melt kneading the combined (a), (b) and (c); (vi) optionally adding (d) at least one unmodified polyolefin, ethylene copolymer or ethylene terpolymer to (a), (b) or (c) or a combination thereof; And (vii) extruding the composition into a strip, film or sheet, powder, profile, or a plurality of beads, flakes, granules, three-dimensional articles, or pellets.

In one embodiment, the polymer composition according to the invention is remelted to form the desired product. In one embodiment, the polymer compositions should be formed into pellets, powders, granules or flakes or another similar bulk form during their initial preparation. This bulk form is very easily transported as is known. Therefore, in one embodiment, the commercialized polymer composition of the present invention is remelted in each bulk, and then is a geotechnical article, such as another article having a sheet, strip, profile or film or 3D form for use in CCS. The desired product such as is formed in the form.

According to another embodiment, the filler, if present, is mixed or synthesized in the composition by a multi screw extruder, in particular a twin screw extruder, at a temperature in the range from 130 to 320 ° C.

The method described above involves the selective use of fillers. In one embodiment, the method uses any of the fillers described or added herein.

According to another embodiment, the filler is melt kneaded with ET and PO using a compatibilizer (magnetic or external) to form a filled compatibilized polymer composition.

According to another embodiment, the filler is first dispersed in the first polymer to form a blend, hereinafter referred to as 'masterbatch'. The masterbatch is then further mixed with ET, PO, functionalized PO or another compatibilizer to form a filled compatibilized polymer composition.

According to another embodiment, the commercially charged filled blend comprises a filler having an average particle size of at most about 80% by weight, specified as below 50 microns, in particular below 25 microns, preferably below 10 microns. Fillers include metal oxides, metal carbonates, metal sulfates, metal phosphates, metal silicates, metal borates, metal hydroxides, silicas, silicates, aluminates, alumino-silicates, chalk, talc, dolomite, kaolin, clay, fibers and whiskers , Metal, metal-coated inorganic fibers, wollastonite, industrial ash, concrete powder and cement, or mixtures thereof.

In one embodiment, the filler is selected from the group consisting of calcium carbonate, dolomite, talc, clay, kaolin, silica, wollastonite, barium sulfate, industrial ash, concrete powder and cement or combinations thereof.

According to another embodiment, the dispersion of ET in PO with the aid of a compatibilizer, conversely the dispersion of PO in ET, and the dispersion of filler in these blends are multi screw extruders, in particular intermeshing multi screw extruders, preferably Is provided by a co-rotated twin screw extruder.

Incorporation of fillers into the composition according to the invention is noted in that it provides certain advantages for commercially available polymer compositions, especially when the compositions are compression molded into strips, membranes or three-dimensional profiles. Compositions containing higher filler additions lower power consumption by the extruder during extrusion of the article and reduce heat buildup because the thermal conductivity of the blend in the melt phase is improved. Surprisingly, when fillers are introduced into the compositions described above, less mechanical energy is required for melt kneading on the mass units of the compound compared to unfilled HDPE or MDPE. Thus, the relative yield increases and the heat buildup in this composition decreases along the extruder. Moreover, since the flowability of EP, in particular polyamide and polyester, is higher than PO, the resistance of the composition to shear during mixing and extrusion is lower than HDPE. As a result, less gel is produced and less degradation of the composition occurs. Thus, the present invention produces thin strips under the same torque of the extruder, so that an increased production rate can be obtained when measured in unit length per unit time. This advantage is particularly important when relatively high molecular weight elastomeric polymers are provided, such as on the PO phase, for example LLDPE, EPR, EPDM, SEBS and ethylene copolymers and terpolymers. With a typical MFI of up to about 0.2 g / 10 min at a load of 2.16 kg at 90 ° C., the composition comprising the high viscosity PO polymer is combined with the most fluid polymer, for example polyamide or polyester such as the ET phase. When melt kneading, the result is a composition that does not resist torque in the extruder, does not tend to gel and degrade in the extruder, and has good melt strength and fast crystallization rate.

In one embodiment, the filler is one having surface treated fillers, in particular hydrophobic surface treatments.

According to another embodiment, the dispersion of filler and polymer is provided in a one step process wherein the polymer (functionalized PO, ET and optionally non-functionalized PO) is fed to the first hopper of the extruder, melt kneaded, The filler is supplied from the second opening of the extruder and melted. The second opening is generally an auxiliary opening with at least one auxiliary supply for the filler. Trapped air and absorbed moisture are removed by at least one atmospheric vent. The mixture is further melt kneaded until some mass is broken up and the filler is evenly dispersed in the polymer. Trapped volatiles such as by-products can be selectively removed by any vacuum hole. The resulting composition is then extruded through a die to form a strip consisting of or comprising pellets, powders, granules, three-dimensional articles or profiles or commercially available polymer compositions.

According to another embodiment, the filler is limited from organic acids, organic esters, oils, polymers, organic amides, organo-metal containing organo-silanes, organo-titanates, organo-zirconates, or combinations thereof Surface treated by a selected formulation without. Surface treated fillers are more easily dispersed and require less mechanical energy. In one embodiment, the filler is surface treated to have a hydrophobic surface, and in yet another embodiment, the filler is surface treated by bonding an organo-metal formulation having a hydrophobic agent.

According to another embodiment, pellets, granules, flakes or powders of a commercially available blend comprising a filled blend are sequentially introduced into a second extruder for remelting and extruding into strips or profiles or sheets, or blown It is introduced into a molding machine to form a blown article or film or sheet, or it is introduced into an injection molding machine to form a molded part, or it is introduced into a compression molding machine to form a molded part.

According to another embodiment, the first extruder for melt kneading of ET, PO, compatibilizers and optionally fillers and / or other additives is a multi screw extruder, in particular a twin screw extruder, for sheet or profile or strip extrusion The two extruders are single screw extruders or twin screw extruders.

According to another embodiment, dispersion is provided in a two step process. At this time, some or all of the polymer is fed to the first hopper of the extruder, melt kneaded, and then the filler is fed from the second opening of the extruder to melt. The second opening is generally an auxiliary-opening with at least one auxiliary feeder for the filler. Trapped air and adsorbed moisture are removed by at least one vapor outlet. The mixture is further melt kneaded until most of the mass is broken up and the filler is evenly dispersed in the polymer. By-products as well as trapped volatiles can be selectively removed by any vacuum outlet. The blend is then pumped through a die to form pellets, beads, plates or powders, which are later provided to a second extruder to mix with the remaining polymer. Blends are hereafter termed 'concentrates'. Concentrates that are part of the polymer and filler may also be popped into the melt directly to the second extruder without cooling and pelleting.

According to the present invention, the introduction of fillers into a commercialized polymer composition is another advantage, in particular when the composition is extruded into a sheet, profile, film, or strip, or when the strip is welded to another strip of the composition, for example by ultrasonic welding. Has This advantage is to introduce filler into the composition at a certain weight percent to improve its weldability, which will be discussed in more detail later in this specification. Moreover, fillers improve the UV and thermal stability of the blends and civil composite articles formed therefrom. The filler may further provide the blend with coloration, eg faint and / or vivid color, and in particular color matching of the constrained GRM.

In one embodiment, the civil composite article comprises an extruded or molded strip having a thickness in a range from about 0.1 mm to about 5 mm. In one embodiment, strips of a given size are strips and sand at a vertical stress of 4 lb / in ² (about 27.58 kPa) compared to strips of a given size formed of pure MDPE or HDPE when tested to ASTM D6706-01. Have at least 10% greater traction.

In one embodiment, the civil composite article includes a friction promoting portion on at least one outer surface of the article. At this time, the friction enhancing portion includes a fabric, embossed, engraved, through hole, finger shaped extension, hair shaped extension, wave shaped extension, coextrusion line, bonded fiber or grain or aggregate, dot, mat or a combination thereof.

According to another embodiment, the strip is provided or included in at least one layer, in one embodiment two or more layers. At least one layer then comprises a commercialized polymer composition or a filled commercialized polymer composition as defined above. Still other layers or layers can be selected without limitation from the compositions defined above or any other composition.

According to yet another embodiment, a heterogeneous multilayer strip is provided comprising at least one layer in addition to at least one layer comprising a commercially available polymer composition of the invention, wherein the heterogeneous multilayer strip is any other polymer composition and blend. It includes. According to another embodiment, homogenous strips are provided comprising commercially available blends in which all layers can be the same or different from one another.

According to another embodiment, a strip is provided comprising at least one layer, in particular at least two layers, wherein the at least one layer is expanded, hydrolyzed and oxidatively decomposed compared to HDPE-based strips having the same dimensions. And small atoms and molecules, both hydroxyl ions, halogens and their ions, free radicals, both of which are resistant to extraction, evaporation or leaching of important additives and low permeability to diffusion through the compound. For the diffusion of anions, cations, hydrocarbons, fuels, bases, compounds containing aromatic rings, compounds containing hetero rings, low boiling organic solvents, and molecules containing VOCs, heavy metals, oxygen, ozone, and acids It includes nano sized particles having high barrier properties. In one embodiment, the small molecule has a molecular weight less than about 1000 Daltons. In one embodiment, the composition further comprises nano sized particles that provide barrier properties for the composition. In one embodiment, for molecules having a molecular weight lower than about 1000 Daltons, the permeability of the composition is about 10% lower compared to compositions comprising the same composition that does not include nanosize particles,

Nano-size barrier particles include nanoclays and their modifications, nano silicas and their modifications, nano silicates and their modifications, nano-alumosilicates and their modifications, nano zinc oxides and their modifications. , Nano-TiO ₂ and its modifications, nano zirconium oxides and their modifications, nano-talcum and their modifications, nano-tubes and their modifications, nano-metal particles and / or flakes and their modifications Inorganic particles coated with water, metals and their modifications, carbon black, nano size sulfides and sulfates and their modifications, nano size natural particles and their modifications, in particular plant or animal origin such as cellulose, lignin, protein It is selected without limitation from the group consisting of the matrix, or combinations of the aforementioned particles.

In one embodiment, the barrier nano size filler is selected from nano clays and modified nano clays.

In one embodiment, the filler is selected from metals and inorganic particles coated with metals, and the layer is characterized by improved electrical conductivity. Conductivity is useful for applications in which electrical charge, current, or potential is generated or delivered along or via an article.

According to yet another embodiment, the nano size clay is introduced in at least one layer at a load of about 0.1 to about 70 weight percent based on the weight of the blend blended. Suitable grades of nano sized clays are commercially available from, for example, Nanocor and Southern Clay products.

In one embodiment, when the at least one layer further comprises an additive selected from HALS, organic UV absorbers, and / or inorganic UV absorbers or combinations thereof, the layers have the same dimensions or have the same additives. At least 10% lower extraction, evaporation and / or hydrolysis rates as compared to the comprising HDPE layer.

In one embodiment, the at least one layer exhibits at least 10% lower weight gain compared to a layer of HDPE having the same dimensions after soaking in n-octane at 25 ° C. for 60 days. Lower intake of the hydrocarbon is due to the cross-linking provided by the polarity of the ET, the barrier properties provided by the filler (optionally nano size filler), and the reaction between the functionalized PO and the functional groups of the ET. This is due to the effect.

In one embodiment, the at least one layer exhibits at least 10% better elongation at break compared to PET layers having the same dimensions after immersion for 60 days at 45 ° C. in an aqueous solution with pH = 11.

In one embodiment, the at least one layer exhibits at least 10% better elongation at break (ETB) retention than the PA6 layer with the same dimensions after soaking at 45 ° C. for 60 days in an aqueous solution with pH = 4. Retention means the final ETB divided by the original ETB.

Compatibilizing blends as defined above include (i) organic UV absorbers and in particular benzotriazoles and benzophenones such as Tinuvin ^™ (manufactured by Ciba) and Cyasorb ^™ (manufactured by Cytec) available commercially; (Ii) inorganic UV absorbers and in particular additives of micro-sized, submicron size and nano-sized particles, for example commercially available SACHTLEBEN Hombitec RM 130F TN ^TM (manufactured by Sachtleben), ZANO ^TM zinc oxide (Umicore), NanoZ ^TM zinc oxide (Advanced Nanotechnology Limited) and zinc oxide AdNano ^{TM TM} titanium oxide and zinc oxide containing a (Degussa); (Iii) carbon black; (Iii) light stabilizers and especially hindered amine light stabilizers (HALS) such as, for example, commercially available Chimassorb ^™ (manufactured by Ciba), Cyasorb ^™ (manufactured by Cytec); Or an additive selected from any mixture thereof.

UV and heat stabilized commercial blends according to one embodiment of the present invention are more resistant to UV light and heat induced degradation compared to HDPE comprising the same additives of the same capacity. The mechanisms behind this feature are slower leaching and / or evaporating UV absorbers and light stabilizers from polymeric articles by moisture and heat, slower diffusion of free radicals due to increased barrier properties and This is because the thermal conductivity in the layer is lower than that due to the improved thermal conductivity. In particular, the leaching rate is slower due to the inherent barrier properties of engineering thermoplastics such as polyamides and polyesters and the improved barrier properties provided by nanoscale barrier fillers. The presence of the fillers according to the invention described above has a positive effect on slowing UV light and thermal induced decomposition due to improved thermal conductivity and thus elimination of heat buildup in the strip and acceleration of the Arrhenius-type temperature dependent decomposition. The presence of the inorganic UV absorber improves durability because the leaching and hydrolysis of the additive is almost zero.

According to another embodiment, the strip comprises two or more parallel layers, wherein at least one layer comprises a stabilizer to protect from UV light and heat induced decomposition.

According to another embodiment, a strip is provided comprising at least one layer, in particular at least two layers, wherein at least one layer comprises a commercial blend of the invention. The strips obtained are useful, for example, in geotechnical applications, in particular CCS.

According to another embodiment, the strips are defined in GRM and in particular soil and peat as compared to strips made of MDPE or HDPE, as tested in the same manner as ASTM D5321-02 or other friction coefficient test standards as defined in one of the above. By the improved friction coefficient.

As defined in one of the above embodiments, the sheet or strip or shaped article is provided by extruding, or molding, the blend of commercialization blends directly from the same extruder used to mix the ET and PO components or from at least one second extruder. Can be.

According to another embodiment, the commercial blend is initially provided by a multi screw extruder. The molten, pelletized or chopped commercial blend is fed to a second extruder, in particular a single screw extruder, and melt kneaded through a die to form a sheet or strip. The final thickness of such strips can vary from about 0.1 millimeters (mm) to about 5 mm or more. In one embodiment, the strip thickness ranges from about 0.5 to about 2.5 mm.

According to another embodiment, improved strips, in particular strips adapted for CCS, are provided. Friction of the strip with constrained GRM is enhanced by introducing one or more friction-promoting portions to at least one outer surface of the strip. Such friction-promoting portions may include engraved fabrics, embossed, holes, finger extensions, hair extensions, wave extensions, fibrous polymer lines, coextruded lines, dots or mats provided from the extruder or by spraying. And combinations thereof. In this way, the GRM can be interlocked with such CCS friction-promoting parts. In another embodiment, friction is enhanced by the introduction of a filler having an average particle diameter greater than about 100 microns. In certain embodiments, the filler is industrial ash, for example ash derived from the combustion of coal. In another embodiment, the compatibilized blend is formed such that its surface is rough and / or porous to improve friction with GRM.

According to another embodiment, the strip or shaped article is colored with a specific GRM color enhanced by the strip and the CCS formed therefrom with pigments and / or dyes. In one embodiment, the strip has a shade of soil; Alternatively colored full color; Alternatively colored in peat color; Alternatively, it is colored in any desired color.

According to another embodiment, the PO and ET components can be adjusted according to the intended use of the CCS. Thus, for example, when CCS is used in desert-like conditions or tropical regions where ambient temperature and sunlight and UV exposure are expected to be much higher than in temperate regions, the relative amount of ET can be increased relative to PO. In one embodiment, the ratio for use in hot areas is a PO 1 ratio to ET 4 ratio to PO 4 ratio to ET 1 ratio. Since PO can easily stretch and weaken at higher temperatures, increasing the ET / PO ratio can enhance strength at such temperatures. On the other hand, when CCS is expected to be used at ambient temperatures that are expected to be lower than temperate regions such as the Arctic Circle, Arctic, Antarctic or Antarctic Regions, on the other hand, it provides better flexibility at such relatively low temperatures. To increase the relative amount of PO. In one embodiment, the ratio for use in cold regions is a PO 1 ratio to ET 1 ratio to PO 10 ratio to ET 1 ratio. Furthermore, in areas where low temperatures are expected in autumn and winter, the PO phase further comprises an elastomeric polymer having a glass transition temperature (Tg) lower than 0 ° C. Therefore, in one embodiment, the compatibilized polymer composition may comprise a polyolefin, ethylene copolymer or terpolymer and at least one engineering to provide creep resistance and warpage modulus suitable for the hardness and / or environmental conditions anticipated in the region where the geotechnical article will be used. The relative amounts of thermoplastics are selected and further included. Similarly, in other embodiments, the relative amounts of additives can be adjusted according to the expected use. For example, high solar UV may include additional UV absorbers and / or HALS. In one embodiment, the PO phase comprises ethylene acrylic acid or methacrylic acid or ester copolymers or terpolymers having higher resistance to UV light compared to HDPE and ET. Examples of such UV resistant polymers are ELVALOY ^™ (manufactured by Du-Pont) and LOTRYL ^™ (manufactured by Arkema), which are commercially available polymers.

According to another embodiment, the strip is assembled into a three-dimensional CCS, which comprises a plurality of strips as defined in one of the above, wherein one strip is connected side by side with its neighboring strip through a separate physical seam, such that The seams are separated from each other by non-joint regions (eg see FIG. 1 described in more detail below). According to another embodiment, the seam is the result of welding, joining, sewing, or any combination thereof. According to another embodiment, the distance between seams measured from the ends of neighboring seams varies within the range of about 50 mm to about 1500 mm. As used herein, the term "about" refers to a range of ± 20% of the defined measurement.

According to another embodiment, the distance between the seams measured from the center of each seam ranges from about 51 mm to 1500 mm or more. In one embodiment, the seam is welded by an ultrasonic device, in particular a pressureless method and means for combining them. In particular, weldability by ultrasonic welding is a significantly improved factor in the CCS manufacturing process according to another embodiment of the invention. In one embodiment, the plurality of extruded strips cut to a predetermined width is welded to form a very durable CCS for GRM restraint.

In one embodiment, the article comprises an extruded or molded strip having a thickness in the range of about 0.1 mm to about 5 mm. In one embodiment, a strip having a given size of 4 lb / in ² (about 27.58 kPa) between the strip and sand, when tested by ASTM D6706-01, compared to a strip of given size formed of pure MDPE or HDPE. Have at least 10% greater traction at normal stress. In another embodiment, the geotechnical article includes a friction-promoting portion at at least one article outer surface, wherein the friction-promoting portion is, for example, fabric, embossed, relief, through hole, finger extended, hair shaped expanded , Wavelike expansion, coextruded lines, bonded fibers or grains or aggregates, dots, mattes or combinations thereof.

In one embodiment, the geotechnical article includes a plurality of strips, each strip leading to neighboring strips in a side-by-side arrangement through separate physical seams, wherein the seams are spaced from each other by non-joint regions. Three-dimensional cellular constraint system (CCS). In one embodiment, the three-dimensional CCS is a containment and / or restraint of a material made of soil, soil, rock, gravel, sand, stone, peat, clay, concrete, aggregate, road construction material and any combination of two or more thereof, and Used for strengthening.

In one embodiment, the seams are provided by welding, joining, sewing, stapling, fixing by riveting, or any combination thereof. In one embodiment, the seam is welded by one or more ultrasonic welding, laser welding and thermostatic welding. In one embodiment, the compositions of the present invention exhibit at least 10% shorter weld cycle times compared to pure HDPE for the same weld dimensions. That is, when articles made from the compositions described herein are welded, the time required to form a suitable weld is reduced by at least 10% in this embodiment.

In one embodiment, a geotechnical article formed or comprising a commercialized polymer composition of the present invention provides weldability, wherein the welding line and the welding spot (eg, separate welds must be within one line). Need not be) in one embodiment, the temperature is from about 40 ° C. to about 70 ° C., and in other embodiments, the temperature may be able to withstand loads for years at temperatures above 40 ° C., from about 40 ° C. to about 60 ° C. have. In one embodiment, a geotechnical article formed from or comprising a commercialized polymer composition of the present invention may withstand such temperatures for a period of time ranging from at least two years to about 100 years. In one embodiment, such geotechnical articles can withstand such temperatures for such periods of time without disruption or significant creep. In contrast to the present invention, geotechnical articles made from prior art materials such as HDPE or MDPE cannot withstand such temperatures during such periods. In one or more such embodiments, such geotechnical articles provide performance that far exceeds the performance of prior art materials such as HDPE or MDPE.

Polyethylene is known to be difficult to weld by ultrasonic welding due to its low density, low coefficient and low coefficient of friction. The new combination of ET and PO provides improved weldability compared to HDPE. The improved weldability described herein is the result of a combination of the above defined properties. Improved weldability is most noticeable in ultrasonic welding. Thus, during ultrasonic welding, high frequencies, for example ultrasonic mechanical vibrations, are transmitted to the mating plastic parts by the ultrasonic welding machine. At the contact points, seams or interfaces of the two parts, the combination of force and surface and / or intermolecular friction applied from the ultrasonic vibrations increases the temperature until the melting point of the thermoplastic material is reached. Ultrasonic energy is then removed and molecular bonding or welding occurs between the two plastic parts. High coefficients of friction and high acoustic conductivity are desirable.

Ultrasonic welding is more efficient in relatively hard and relatively amorphous materials.

Ultrasonic welding systems generally include a high frequency power supply, usually 20-40 kHz. The high frequency energy is directed to a horn, also known as a sonotrode, that transmits mechanical vibrations to the target to be welded.

Surprisingly, according to the methods defined herein, if ET and PO are blended, including compatibilizers, especially if the commercialized blend further comprises fillers, unfilled HDPE-based strips and unfilled with similar dimensions Weldability is significantly improved over PO-ET blends. As the surface melts, the speed at which the surface recovers its strength, final weld strength, and its load bearing capacity for a long time at elevated temperatures is improved.

The proposed mechanism is shown in the following manner in a non-limiting manner, such as synergistic weldability: higher elastic modulus and lower acoustic damping, i.e. a tighter ET characterized by creep coefficient, loss factor and dissipation factor. The rich phase reacts faster to ultrasonic vibrations and heats the PO rich phase with a lower melting point to form welds faster than when welded with HDPE alone. The presence of fillers in such polymer phases, especially in ET-rich phases, increases the modulus, coefficient of friction and sound velocity in the phases. During the subsequent cooling phase, the ET-rich phase crystallizes faster than the PO-rich phase, resulting in shorter cycle times. During the cooling step, the filler acts as a nucleating agent. The presence of fillers, especially submicron particles and nano-sized particles, improves the rate of nucleation of both ET and PO phases, resulting in welds becoming much faster than unfilled HDPE or MDPE or incompatible PO-ET blends. It becomes durable.

In one embodiment, if two strips are joined by welding, the final weld strength measured after 48 hours of welding at ambient temperature of the two strips welded together according to the invention is about 1300 N per 100 mm weld width. Greater than

In another embodiment, if the two strips are joined by welding, the final weld strength measured after 48 hours of welding at −20 ° C. of the two strips welded together according to the invention is about 1600 N per 100 mm weld width. Greater than

In one embodiment, if the two strips are joined by welding, the final weld strength measured after 48 hours of welding at ambient temperature of the two strips welded together according to the invention is about 2000 N per 100 mm weld width. Greater than

In another embodiment, if the two strips are joined by welding, the final weld strength measured after 48 hours of welding at −20 ° C. of the two strips welded together according to the invention is about 2400 N per 100 mm weld width. Greater than

In one embodiment, if two strips are joined by welding, the final weld strength of the two welded strips at -20 ° C is greater than about 1000 N per 100 mm weld width.

In one embodiment, if two strips are joined by welding, the final weld strength of the two welded strips at 70 ° C. is greater than about 1000 N per 100 mm weld width.

For example, as indicated above, in one embodiment, it is important to improve weldability with the commercialized polymer compositions of the present invention, which is an important and integral part of the product integrity of articles formed in accordance with the present invention. to be. In articles such as CCS, the points at which the parts are welded together are weak points and the formation of such welds, in particular the formation of high quality welds, is a time consuming process. The new commercialized polymer compositions provide better thermal and sound conductivity so that welding, in particular ultrasonic welding, is faster and as a result welding is more continuous, stronger, and more under the continuous load types experienced by geotechnical articles and in particular by CCS. Good performance, longer lasting All these improvements come from the commercialized polymer compositions according to the invention.

In one embodiment, some of the geotechnical articles include reinforcing structures suitable for use in attaching the article to the substrate for use such as CCS. That is, when used, for example, CCS must be fixed to the ground or other substrate (see FIGS. 1, 3 and 6 below). Generally, for example, a pile in the form of a short length rebar, spike, angle-iron or polymer material (including in one embodiment the commercially available polymer composition of the invention) Stake or wedges are used to secure the CCS to the floor. The physical form of such piles or wedges is known in the art. Therefore, in one embodiment of the present invention, a geotechnical article such as CCS is formed of a commercialized polymer composition and used in combination with wedges and tendons. Tendons in one embodiment, and wedges in another embodiment, and both wedges and tendons in another embodiment are also formed from polymer blends commercialized according to the present invention. Therefore, although wedges and tendons are known in the art, the present invention encompasses combinations of geotechnical articles comprising polymer compositions formed or commercialized from commercially available polymer compositions as described in the specification by combination with wedges and tendons. In other embodiments, the geotechnical article, and one or both of the wedge and tendon, comprise a polymeric composition formed or commercialized from the commercially available polymer compositions of the present invention.

In one embodiment, the point where the pile contacts the CCS is reinforced. In one embodiment, the reinforcing structure provides for increased strength, increased resistance to collapse due to contact with the materials used to adhere to the substrate, increased resistance to UV, increased resistance to elevated temperatures, or increased resistance to thermal expansion. A commercially available polymer composition having a proportion of at least one polyolefin, ethylene copolymer or terpolymer, relative to at least one engineering thermoplastic material, adjusted to provide at least one of. Thus, in one embodiment, an additional layer of geotechnical article is provided at a general location where the pile will be used to secure the geotechnical article to the ground (see FIG. 6 below). In one embodiment, the additional layer includes a ratio of PO and ET that is different than that used for the rest of the CCS to increase strength and / or resistance to environmental influences. For example, increasing the relative amount of ET will provide improved strength. As in other embodiments, piles are often made of iron (eg, the riba) and iron will absorb more heat than geotechnical articles at solar and / or high temperature conditions. This heat can be transferred to the article and weaken the article at and near the point of contact. Therefore, the reinforcement can improve the resistance to elevated temperatures reached by the piles in contact. As will be appreciated, the degree of adjustment of the ratio of PO to ET is somewhat limited because the preferred features derived from the combination of components of the commercialized polymer composition are still important in the reinforced part of the article.

Description of Embodiments Illustrated in the Drawings

1 is a perspective view of a single layer CCS 10 that includes a plurality of welded strips, wedges, and tendons in accordance with embodiments of the present disclosure. 1 shows the CCS 10 reinforced by tendons 12. The CCS 10 comprises a plurality of strips of plastic 14 that are bonded, sewn or welded together, in particular ultrasonically welded, wherein one strip is joined in an equally spaced joining region 16 alternately with The cell walls 18 of the individual cells 20 are formed. The pairs of strips 14 are paired in such a way that, for example, the outer strips 22 begin to pair with the inner strip 24 and continue to the next two inner strips 24. Each such pair is joined, for example, in the bonding region 16. As shown in the left end of FIG. 1 showing the end of the CCS, the joining region 16 includes a weld point 26 adjacent the end 28 of each strip 14. At the end of the CCS a short tail 30 between the end 28 of the strip 14 and the outer weld 26 is provided to stabilize the fragment of the strip 14 adjacent to the outer weld 26. Each strip pair is welded to each other at an additional joining region 16 to produce strip segments of approximately equal length between the outer weld points 26. In addition to these welds, each strip 14 (except for the outermost strip) from each pair of adjacent strips 24 may also be used at the midpoint 32 for the strip adjacent to the midpoint of the weld in the strip pair. Are welded. As a result, when a plurality of strips 14 extend in a direction perpendicular to the strip plane, the plastic strips are bent in a sinusoidal shape to form a web of cells 20, referred to herein as a repetitive cell pattern. Each cell 20 of the cell web has a cell wall made from one strip and a cell wall made from another strip.

As can be seen herein, the commercialized polymer composition according to the present disclosure provides enhanced weldability in one embodiment, which is an enhancement and / or improved weld strength of welds formed with the compositions of the present disclosure as compared to welds formed with prior art materials. It will include. Such strengthened and / or improved weld strength is important not only for a period of time over the years of use of articles made with the composition, but also during installation of articles such as geotechnical articles and CCS. The weld point is therefore subject to high stress at one or more points, examples of which include (1) compression of the item by the GRM held by the item during installation; (2) expansion of GRM during periods of high humidity; (3) expansion of the GRM during the freeze / thaw cycles of the water contained in the GRM; (4) thermal mismatches between structures of articles such as GRM and CCS walls (eg, from different CTEs).

In the embodiment shown in FIG. 1, the holes 34 in certain strips 14 are adjacent to the joining region 16 or 32. Each tendon 12 extends through a series of substantially matching holes 34. The tendon 12 acts as a continuous, integrated fixing member that reinforces the cell web and prevents the web from leaving undesirably, thereby improving stability in web installation. It should be noted that the CCS shown in FIG. 1 includes tendons, but tendons are not always required or used in CCS. For example, tendons may be unnecessary where wedges (described below) are used and tendons may be unnecessary where CCS is not moving. Tendons can be used in waterways and slope applications to provide additional stability against gravity or hydrodynamic forces and may be needed when piles are not available due to lower layers or inherently hard soil / rock.

The CCS embodiment shown in FIG. 1 further includes a wedge 36, which is used in attaching the CCS to a substrate to which it is applied, such as ground. The wedge 36 is inserted into the substrate to a depth sufficient to support holding the CCS in position. The wedge 36 may take the form of any wedge known in the art using CCS. In one embodiment the wedge 36 is simply a cut of iron or steel ribs to a suitable length. In another embodiment, the wedge 36 is formed of a polymeric material. In another embodiment the wedge 36 is formed from any of the compatibilizing polymer compositions as shown in the present disclosure for the CCS itself. In one embodiment the composition of the wedge 36 may be the same commercialized polymer composition as in the CCS in which the wedge is used and in another embodiment the wedge composition is different from the composition of the CCS in which the wedge is used. In one embodiment the wedge is formed of a composition having a higher rigidity, for example obtained by loading more of the ET component. In one embodiment the wedge is formed of a composition with a higher hardness obtained, for example, by employing different polymers or blends of polymers for the ET component of the composition.

Additional holes 34 may be included in the polymer strip as described in US Pat. No. 6,296,924. The additional holes increase frictional interlock with GRM by 30%, increase root lock-up with vegetated system as roots grow between cells 20 and It also improves lateral drainage through strips, providing better performance in soggy soils and promoting a healthy soil environment. You can also reduce installation and long-term maintenance costs. In addition, such CCSs are lighter and easier to handle than CCSs with solid walls.

2 is a perspective view of a single cell 20 of CCS formed or comprising a commercially available polymer composition containing GRM in accordance with embodiments of the present disclosure. The CCS cell 20 shown in FIG. 2 is depicted as appearing when the CCS is located on an inclined plane (direction indicated by arrow A) where the GRM held in the cell is arranged substantially horizontally while the walls of the CCS are It is arranged perpendicularly to the inclined surface where is located. As a result, the CCS and its cell 20 are tilted towards the observer. Thus, the walls 14 of the CCS are not arranged vertically and are roughly perpendicular to the surface of the substrate and thus on the up-slope side of the CCS by filling the inclined CCS as shown in FIGS. 2 and 3. Will leave an "empty area".

The cell 20 depicted in FIG. 2 receives the forces F1 and F2 at the side wall 14 and the force F3 at the welding point. As a result of the tilt and the blank area described above, the forces F1 and F2 applied to the walls of the CCS are not balanced. On the proximal side of the cell 20, GRM fills the cell to the upper edge and exerts a force F1 against the wall from the inside. The GRM in the cell 20 and the GRM in the adjacent lower slope cell (not shown in FIG. 1) exert a force F2 in the upward direction of the slope. Force F2 is smaller than force F1 because of the empty area. This unbalanced force causes failure in prior art welding, especially when the temperature of the CCS wall exceeds about 40 ° C., or when fuel and organic fluid are in contact with the CCS. There is therefore a strong need for polymer compositions, such as the commercialized polymer compositions disclosed herein, that provide greater strength, good thermal and chemical stability, and improved weld dependence.

As shown in FIG. 2, the force F3 originates in the GRM and tends to exert a separating force on the weld point 16. The force derived from the GRM is derived from its mass and / or from the expansion of the GRM and / or from the repeated heat-cooling cycles, for example during repeated freeze-thaw cycles. Damage resulting from these two physical forces can be further accelerated when hydrocarbons such as fuels and organic fluids come into contact with the CCS. While the water contained in the GRM freezes, the GRM expands and pressurizes against the wall 14 and the weld 16, after which the GRM relaxes upon cooling and “fills up” to any of the expansion regions caused by the pressure. The relaxation then continues, with GRM expanding again during the next freeze cycle. This shows both the results of the freeze-thaw cycle on the CCS and the pressure applied to the weld 16 and indicates the importance of strong welding between adjacent strips forming the CCS.

FIG. 3 is a perspective view showing a single cell 20 of CCS made of or comprising a commercially available polymer composition, which includes GRM in FIG. 2 and also includes wedges 36 as described with respect to FIG. 1. In accordance with another embodiment of the disclosure. 3 shows the force applied to the CCS and to individual cells 20 including wedges 36. As shown in FIG. 1, not all cells in the CCS include a wedge 36. A sufficient number of wedges 36 are used to help the CCS maintain its original position on the substrate to which the wedge is applied.

As shown in FIG. 3, the forces F1 and F2 (as described above with respect to FIG. 2) continue to exist in FIG. 3 and exert substantially the same pressure on the cell 20 as described above. In the embodiment shown in FIG. 3, a wedge 36 has been added, which is added to force F2 to balance force F1 by applying a force designated F4 to keep CCS in position. As can be seen, the presence of the wedge 36 exerts a force F4 on the portion where the upper wall 14 is located directly. The increased localized pressure is not strong enough and creep resistance can have a detrimental effect on the wall. If the CCS walls are chemically sensitive to oil and fuel, such as in the case of HDPE or MDPE, the walls become weaker, more flexible and more succumbing at such localized and unusual stress concentration points. In one embodiment described below with respect to FIG. 6, the top wall is reinforced by the addition of an auxiliary wall portion to mitigate the deleterious effects that ubiquitous pressure from the wedge 36 may have on the top wall 14. .

4 is a perspective view showing a single cell 20 of CCS made of or comprising a compatibilizing polymer composition, including tendons 12 and according to another embodiment of the present disclosure. As described in connection with FIG. 1, tendon 12 passes through wall 14 in hole 34. The tendon 12 is used to help keep the CCS in its intended position, especially in applications where wedges are prohibited or cannot be used because of the restrictions imposed by the substrate. For example, tendons can be used in applications where the CCS is located on the geomembrane, preferably not penetrating the geomembrane with a wedge. As shown in FIG. 4, tendon 12 stresses wall 14 in the vicinity of hole 34. This stress can cause damage to the wall 14, which may cause the CCS to fail. In one embodiment, tendon 12 is simply a cut to the right length of the rebar. In another embodiment tendon 12 is formed of a polymeric material. In another embodiment the tendon 12 is formed of any of the compositions as shown in the present disclosure for the CCS itself. In one embodiment the composition of tendon 12 may be the same composition as in CCS in which tendon is used and in another embodiment the composition of tendon is different from the composition of CCS in which tendon is used. In one embodiment the tendon 12 is formed of a composition with a higher strength, for example obtained by loading more ET components. In one embodiment the tendon 12 is formed of a composition with a higher strength obtained by employing different polymers or blends of polymers, for example for the ET component of the composition.

FIG. 5 is a perspective view of a single cell 20 of CCS formed of a polymer composition or comprising the stomach composition and comprising tendons 14 and lockers 38 in accordance with one embodiment of the present invention. The locker 38 is provided to spread the force of the stress applied to the wall 14 by the tendon 16. Such diffusion results in reduced pressure per unit area of the wall 14. The locker 38 may be formed of any suitable material. In one embodiment, the locker 38 is formed of a composition according to the polymer composition of the present invention mentioned herein. In one embodiment the locker 38 comprises the same polymer composition as in the CCS in which the locker is used, and in another embodiment the locker 38 comprises a different polymer composition in the CCS in which the locker is used. In one embodiment there is provided an ET component which contains a high content of the ET component when the polymer composition of the rocker is different and provides a higher strength than in the CCS used. The rocker provides a means of transferring the stress between the tendon and the walls of the CCS through which the tendon passes. By using the locker 38, the force transmitted from the tendon to the wall of the CCS can be diffused. The walls of the CCS formed of or comprising the commercially available polymer compositions of the present invention are very strong as detailed herein, and the use of the locker 38 can further protect against long term failure.

FIG. 6 shows a single cell 20 of CCS formed of a commercially available polymer composition or comprising a stomach composition and comprising a wedge 36 and a reinforced wall portion 40 in accordance with another embodiment of the present invention. Perspective view. The reinforcing wall 40 serves the tendon 12, like the rocker 38, spreads and distributes the pressure due to the force exerted on the wall 14 by the wedge 38. The embodiment shown in FIG. 6 includes a reinforcing wall 40 having a size significantly larger than the wedge 36. In other embodiments, the reinforcement walls 40 may be of different sizes, smaller or larger than those described by those skilled in the art using CCS. In one embodiment the reinforcement wall 40 extends the entire width of the strip that forms the wall 14 to which it is attached, and in another embodiment the reinforcement wall 40 is less than the full width of the wall 14 or It can be greatly extended. In one embodiment, the reinforcing wall portion 40 extends beyond the top of the wall 14 and folds against the far side of the wall 14, further increasing the strength of the entire wedge contact of the wall of the CCS.

In one embodiment, the reinforcing wall 40 is attached to the wall 14 with a suitable adhesive, such as a pressure sensitive adhesive or a curable adhesive. In one embodiment, the reinforcing wall portion 40 may be attached to the wall 14 by performing a welding operation, specifically ultrasonic welding, or sewing, in situ. In another embodiment, the reinforcing wall portion may be attached to the wall 14 at the same time the weld points 16 and 26 are formed.

The reinforcement wall 40 may be formed of any suitable material. In one embodiment, the reinforcing wall 40 may be formed from any of the compositions disclosed herein for use in the CCS itself. In one embodiment, the composition of the reinforcing wall 40 may be the same composition as in the CCS where the reinforcing wall 40 is used, and in another embodiment the composition of the reinforcing wall 40 is in the CCS where the reinforcing wall 40 is used. Is different from In one embodiment, the reinforcing wall 40 is formed of a composition with higher rigidity, such as obtained by high load ET components. In one embodiment, the reinforcing wall 40 is formed of a composition with higher stiffness, such as obtained using different polymers or polymer blends for the ET component of the composition.

In one embodiment, the reinforcement wall 40 may be used in place of the locker 38. That is, the reinforcement wall 40 may include a hole 34 through which the tendon 12 may pass. In another embodiment, the combination of rocker 38 and reinforcement wall 40 may be applied with tendons 12. Such a combination can be applied, for example, when it is anticipated that a particularly high stress will be applied to the walls of the CCS during the use of the CCS.

In one embodiment, the layer or strip, or article formed therefrom, further comprises at least one additional layer attached to, or coextruded with, the at least one layer. In that one embodiment, the additional layer comprises (1) a combination of the components (a), (b) and (c) and may be the same or different from the composition of the at least one layer, or (2) It may contain a material different from the composition containing said (a), (b) and (c). Thus, additional layers may comprise the same composition, or different compositions, within the scope of the present disclosure, and the additional layers may include other kinds of materials, such as another polymer, or other structures suitable for the reinforcement required.

7 schematically depicts one embodiment of the present invention, wherein the strip 14 made according to one embodiment of the commercially available polymer composition of the present invention further comprises an outer layer 42. The outer layer 42 may be attached or adhered to the strip 14 by lamination or coextrusion or by an adhesive. The outer layer 42 may be composed of any suitable material. In one embodiment, the outer layer 42 comprises a polymeric material. In one embodiment, the outer layer 42 comprises a compatible polymer composition according to the present invention. In one embodiment, the outer layer 42 comprises a compatible polymer composition according to the present invention but with different combinations of PO, ET and compatibilizers. In one embodiment, outer layer 42 includes a polymeric material forming a barrier layer. The barrier layer can be, for example, improved chemical resistance (e.g., ultra-thin coating or deposit such as parylene, plasma polymer, or inorganic layer), improved UV resistance, improved heat resistance, and / Or improved friction with GRM. Thus, in one embodiment, the outer layer 42 may be formed of any of the compositions disclosed herein for use of the CCS itself. In one embodiment the composition of the outer layer 42 may be the same composition as in CCS where tendons are used, and in another embodiment the composition of the outer layer 42 is different than in CCS where tendons are used. In one embodiment, the outer layer 42 is formed of a composition with higher stiffness, such as obtained by high load ET components. In one embodiment, the outer layer 42 may be formed of a composition with higher stiffness, such as obtained using different polymers or polymer blends for the ET component of the composition.

FIG. 8 schematically depicts one embodiment of the present invention wherein a strip 14 made according to one embodiment of the commercially available polymer composition of the present invention comprises a first outer layer 42 disposed over the strip, and It further includes a second outer layer 44 disposed opposite it. The outer layers 42 and 44 may be attached according to the embodiment shown in FIG. 7 as described above, and may include any of the materials described above according to the embodiment shown in FIG. In one embodiment the second outer layer 44 is formed of the same material as in the first outer layer 42, and in another embodiment the second outer layer 44 is different from the first outer layer 42. It is formed of a material.

Materials for use in each of the CCS, tendons, wedges and reinforcement walls can be appropriately selected by those skilled in the art based on the foregoing description. In one embodiment, the material may be appropriately selected as taught herein based on the geographic location of where the CCS is used, more specifically based on the known expected maximum temperature to which the CCS is exposed, and the amount of sunshine to which the CCS is exposed. Can be. As described above, in one aspect may be determined based on the latitude of the CCS usage.

In one embodiment, the civil composite article is a geomembrane. In one embodiment, the geomembrane comprises a plurality of sheets welded or joined together at their respective ends. In one embodiment, the geomembrane comprises (a) acids, bases, oils, fuels, heavy metals, dioxins, oxygen, nitric acid (salts), SOx, NOx, fluorocarbons, organophosphorus compounds, herbicides, pesticides, halogens, halogens Low permeability to one or more of organic solvents associated with acids, ammonia, bacteria, viruses and HDPE geomembranes having the same dimensions; (b) retain at least 10% improved modulus of elasticity when exposed to hydrocarbons and fuels associated with HDPE geomembrane having the same dimensions; And (c) at least one of a load of 20% yield stress and at least 20% high creep coefficient at 60 minutes loading time, measured at 60 ° C. according to ISO 899-1 in relation to HDPE geomembrane having the same dimensions. One or more sheets having;

9 and 10 schematically illustrate four processes for preparing a polymer composition in accordance with the present invention. Referring to FIG. 9, two embodiments are shown in which an external compatibilizer is used.

In process A of FIG. 9, the external compatibilizer is combined with an engineering thermoplastic and the mixture is melt kneaded in an extruder to form the polymer composition product described herein. The process optionally includes melt kneading together the external compatibilizer and one or more optional components of the engineering thermoplastic. In the embodiment described in Process A, the at least one functional group containing polymer or oligomer comprises an external compatibilizer.

In the first step of process B of FIG. 9, the unmodified polyolefin, ethylene copolymer or terpolymer is combined using a functional group containing unsaturated reaction, and the free radical initiator and these components in the extruder are melt kneaded to form a functional group containing unsaturated portion ( moeity) is grafted onto the unmodified polyolefin, ethylene copolymer or terpolymer, as a result of which an external compatibilizer is formed and collected in a solid phase such as pellets. In a second step, the external compatibilizer prepared above is combined with an engineering thermoplastic and the mixture is melt kneaded in an extruder to form the polymer composition product described herein. The process optionally includes melt kneading together the external compatibilizer and one or more optional components of the engineering thermoplastic. In the embodiment described in Process B, the at least one functional group containing polymer or oligomer comprises an external compatibilizer.

Referring to FIG. 10, two embodiments are shown in which a magnetic compatibilizer is formed and used immediately to prepare a composition according to the present invention.

In the first step of process C of FIG. 10, the unmodified polyolefin, ethylene copolymer or terpolymer is combined using a functional group containing unsaturated reaction, and the free radical initiator and these components in the first extruder are melt kneaded to form a functional group containing unsaturated The portion is grafted onto the unmodified polyolefin, ethylene copolymer or terpolymer, resulting in the formation of a self compatibilizer in the first extruder. The self compatibilizer is then combined with the engineering thermoplastics in the molten state in a second extruder, in one embodiment in this case these components are melt kneaded to form the product. In such embodiments, the process optionally includes melt kneading together the self compatibilizer and one or more optional components of the engineering thermoplastic. When carried out by adding the optional components simultaneously with the addition of the engineering thermoplastics, all of these components may be melt kneaded in a second extruder to form the product, as indicated by arrow (1) of process C. In an alternative embodiment of Process C, an optional component may be added to the process after the engineering thermoplastic has been melt kneaded with the self compatibilizer, in which case the optional component is indicated by arrow (2) of Process C. It may be melt kneaded with the product of the second extruder in the third extruder to form the product.

In process D of FIG. 10, the entire process is carried out in a single extruder. In the first part of the extruder of this embodiment, the unmodified polyolefin, ethylene copolymer or terpolymer is combined using a functional group containing unsaturated reaction and the free radical initiators and their components are melt kneaded so that the functional group containing unsaturated part is not modified. Which is grafted onto the polyolefin, ethylene copolymer or terpolymer, which results in the formation of a self compatibilizer in the first part of the extruder. Subsequently, in the second downstream part of the same extruder, the molten engineering thermoplastic is fed into the extruder through a suitable inlet and combined with the newly formed self-compacting agent in the second extruder. In the second part of the extruder, these components are melt kneaded to form the product. In the embodiment described in process D of FIG. 10, the process optionally includes melt kneading together the one or more optional components of the self compatibilizer and the engineering thermoplastic. These optional components may be added simultaneously with, or before or after the addition of the engineering thermoplastics. These components are melt kneaded in the same extruder to form the product, as shown by process D in FIG. 10. It should be noted that the external compatibilizers that can be used in addition to the self compatibilizers formed in the embodiments of these processes in accordance with the present invention are among the optional components in the embodiments shown in both processes C and D of FIG.

The following is a brief description of the drawings, which are intended to describe exemplary embodiments disclosed herein and are not intended to limit the embodiments.

1 is a perspective view of a CCS comprising a plurality of welded strips, wedges and tendons, according to an embodiment of the invention.

2 is a perspective view of a single cell of CCS containing GRM.

3 is a perspective view of a single cell of CCS containing GRM and including wedges.

4 is a perspective view of a single cell of the CCS including a gun and a locker.

5 is a perspective view of a single cell of the CCS including the gun.

6 is a perspective view of a single cell of a CCS including a wedge and a reinforced wall portion, according to another embodiment of the present invention.

7 and 8 schematically illustrate two further embodiments of the present invention, wherein one or two outer layers are laminated or coextruded with a strip comprising the compatibilizing polymer composition of the present invention.

9 and 10 schematically illustrate four procedures for preparing the polymer composition according to the present invention.

For simplicity and clarity of description, it will be understood that the elements depicted in the figures are not necessarily drawn to scale. For example, the dimensions of some of the elements have been enlarged proportionally to one another for clarity. In addition, in order to indicate corresponding elements, the appropriate reference numbers considered here are repeated in the figures.

Welding Test Example

For one embodiment of the present invention, the resistance to long term loading exhibited by welding strips formed from commercially available polymer compositions according to the present description is described in Table 1. Each pair of strips 100 mm wide is welded over an entire width of 100 mm by ultrasonic sonotrode at 20 MHz, and the loads shown in Table 1 apply for these welded 10 pairs at ambient temperature. Measure the portion of the weld pair that remains intact over the number of days the load indicated is applied. As can be seen from Table 1, the materials of the present invention provide higher and improved weld strength and durability compared to prior art materials such as HDPE or MDPE.

Table 1 Melt Test Results

Duration (days)  77 kg load 88 kg load 100 kg load 10 days from 1st All 10 pairs remain intact All 10 pairs remain intact All 10 pairs remain intact 20 days from 1st All 10 pairs remain intact At least 9 pairs remain intact At least 8 pairs remain intact 30 days from 1st All 10 pairs remain intact At least 8 pairs remain intact At least 6 pairs remain intact

By comparison, when the same test was performed using HDPE weld strips with the same width and thickness, the failure rate compared was from 30 days at 77 kg to about 20% and 30 days at 88 kg About 40% and greater than 65% at 30 days under 100 kg conditions.

Example 1-4:

Example 1 Compatibilized Polymer Compositions, Strips and Weld Strips Formed from the Invention

Step 1: functionalize HDPE

1000 g of polyethylene resin Dowlex ™ 2344 from DOW, 1.2 g of dicumyl peroxide and 15 g of maleic anhydride are dry blended. The mixture is fed to the main hopper of an idling twin screw extruder with a length to diameter ratio (L / D) of 40 at 100-200 RPM screw speed and melt kneaded at 180-220 ° C. until a functionalized polymer is obtained. . This polymer is used as a self compatibilizer in the examples, hereinafter referred to as MA-PE.1.

Step 2: Synthesis of Hydrolytic Stability and UV-Protective Compounds

500 g of MA-PE.1, 500 g of PA6 resin Ultramid ™ B50L 01 from BASF, are fed to an idle twin screw extruder with an L / D of 40 at 100-300 RPM screw speed and melt kneaded at 280 ° C. From the auxiliary feeder, 180 g of Talc lotalk Superfine ™ from Yokal, 4 g of Tinuvin ™ 111 and Tinuvin ™ 234 from Ciba, and 10 g of Stabaxol ™ P200 from Rhein Chemie are supplied. The resulting compound is extruded, pelleted with a strand pelletizer and dried at 45 ° C.

The resulting product (hereinafter referred to as CB.1) is extruded into strips 1.5 mm thick and 100 mm wide.

Tensile strength, modulus and creep coefficient are measured after one week of extrusion (hereinafter referred to as T.0) and after exposure for 60 days in an aqueous solution having pH = 6 at 45 ° C (hereinafter referred to as T.60). Surface gloss and chalking are measured after 10,000 hours with QUV (QUV / Spray Method, UVA-340 lamp).

Two strips, each 100 mm wide, are welded with an ultrasonic sonotrode at 20 MHz. Final weld strength is measured 48 hours after welding, hereinafter referred to as UWS.

A pair of strips each having a width of 100 mm is welded (welding width 100 mm), and 10 pairs of welded strips are loaded with 88 kg for a period of 30 days. The percentage of weld pairs that remain intact and is referred to hereinafter as% WCS88.

Resistance to organic fluids is assessed by soaking in diesel fuel for 60 days and calculating the resulting weight gain.

The results are summarized in Table 2.

Example 2: Compositions, strips and welding strips thereof according to US Pat. No. 6,875,520 as comparative examples (not according to the invention)

Step 1: Functionalization of Ethylene-Methyl Acrylate Copolymer

1000 g of ethylene-methyl acrylate copolymer Lotryl ™ 29 MA 03 from Arkema, 1.2 g of dicumyl peroxide and 15 g of maleic anhydride are dry blended. The mixture is fed to an idling twin screw extruder and melt kneaded at 220 ° C. until a functionalized polymer is obtained. This polymer is used as a self compatibilizer in the Examples, hereinafter referred to as MA-LOT.1.

Step 2: Synthesis of PA-MA.LOT.1 Compound

500 g of MA-LOT.1 and 500 g of PA6 resin Ultramid ™ B50L 01 manufactured by BASF are fed to an idling twin screw extruder and melt kneaded at 280 ° C. The compound is extruded, pelletized with a strand pelletizer and dried at 45 ° C.

The resulting product (hereinafter referred to as CB.520.) Is extruded into strips 1.5 mm thick and 100 mm wide.

Tensile strength, modulus and creep coefficient are measured after one week of extrusion (hereinafter referred to as T.0) and after exposure for 60 days in an aqueous solution having pH = 6 at 45 ° C (hereinafter referred to as T.60). Surface gloss and chalking are measured after 10,000 hours with QUV (QUV / Spray Method, UVA-340 lamp).

Two strips, each 100 mm wide, are welded over the entire width with an ultrasonic sonotrode at 20 MHz. Final weld strength is measured 48 hours after welding, hereinafter referred to as UWS.

A pair of strips each having a width of 100 mm is welded over the entire width of 100 mm, and a 10 kg welded strip is loaded with 88 kg over a period of 30 days. The percentage of weld pairs that remain intact and is referred to hereinafter as% WCS88.

Resistance to organic fluids is assessed by immersing the sample of material in diesel fuel for 60 days and calculating the resulting weight gain.

The results are summarized in Table 2.

[Table 2] Comparison of Blend Durability

Example 1 Example 2 characteristic  CB.1  CB.520 Tensile Strength at T.0 (MPa)  43  22 Tensile Modulus at T.0 (MPa)  2600  457 Elongation at Break in T.0 (%)  180  225 Tensile Strength at T.60 (MPa)  40  20 Tensile Modulus at T.60 (MPa)  2000  332 Elongation at Break in T.60 (%)  125  25 Surface characteristics after 10,000 hours with QUV (visible)  Gloss slightly loss, no crack  Surface is etched and contains cracks and voids UWS (N)  2153  1200 % WCS88 (%)  90  60 % Weight increase in diesel fuel
(60 days at 45 ° C)  4  35

Example 3: Compatibilized polymer compositions, strips and welding strips thereof according to the present invention having improved thermal stability and improved puncture resistance at -20 ° C.

Step 1: Synthesis of Hydrolytic Stability and UV-Protective Compounds

200 g of Bondyram 4001 maleated LLDPE from Polyram, 200 g of LLDPE resin LL1001 ™ from ExxonMobil, 300 g of Exact ™ 203 from ExxonMobil, 300 g of PET reclaimed from drinking water bottles, 2 g of Irganox ™ B900 from Ciba, 5 g of CYASORB ™ UV-4042 from Cytec and 5 g of Tinuvin ™ 494 from Ciba are fed to an idling twin screw extruder and melt kneaded at 280 ° C. The compound is extruded, pelletized with a strand pelletizer and dried at 45 ° C.

The resulting product (hereinafter referred to as CB.3) is extruded into strips 1.5 mm thick and 150 mm wide.

After one week of extrusion (hereinafter referred to as T.0), the tensile strength, modulus, and creep coefficient are measured at 75 ° C (hereinafter referred to as # 75) and at -20 ° C (hereinafter referred to as # -20). Surface gloss and chalking are measured after 10,000 hours with QUV (QUV / Spray Method, UVA-340 lamp).

Two strips, each 100 mm wide, are welded over the entire width with an ultrasonic sonotrode at 20 MHz. Final weld strength is measured 48 hours after welding, hereinafter referred to as UWS.

UWS are compared at ambient temperature, 75 ° C and -20 ° C.

A pair of strips each having a width of 100 mm is welded over the entire width of 100 mm, and a 10 kg welded strip is loaded with 88 kg over a period of 30 days. The percentage of weld pairs that remain intact and is referred to hereinafter as% WCS88.

The results% WCS88 at ambient temperature, 75 ° C. and −20 ° C. are compared and the results are shown in Table 3.

Table 3 Summary of CB.3 Characteristics

characteristic CB.3 at ambient temperature CB.3 at 75 ° C CB.3 at -20 ° C Tensile strength (MPa) 28 24 40 Tensile Modulus (MPa) 1300 1000 1800 Elongation at Break% 300 320 180 Surface characteristics after 5,000 hours with QUV (visible) Gloss slightly loss, no crack NA NA UWS (N) 1900 1200 1900 % WCS88 90 80 90

Example 4:

Five high efficiency mixtures, INV1-INV5 and a reference mixture (UV stabilized HDPE), are prepared. Their composition is shown in Table 4. Each mixture also contains a 0.5% TiO ₂ pigment, Kronos ™ 2222 from Kronos and 0.2% PV Fast Brown HFR ™ brown pigment from Clariant. The polymers, additives and pigments are fed to the main hopper of an idling twin screw extruder with an L / D of 40 at a 100-300 RPM screw speed and run at 100-400 RPM at a barrel temperature of 260-285 ° C. The polymer is melted and the additives are dispersed by at least one keading zone. Filler is provided from the auxiliary feeder. Steam and gas are removed by the atmospheric outlet, and the product is extruded and pelletized into strand pelletizers.

TABLE 4 COMPOSITION OF POLYMER

ingredient INV1 INV2 INV3 INV4 INV5 Reference MA functionalized HDPE (kg) 100 100 70 40 40 100
Pure HDPE,
Not functionalized LLDPE (kg) 0 0 0 30 0 0 Ethylene-acrylate (kg) 0 0 0 0 30 0 PET (kg) 30 30 30 30 30 0 Talc (kg) 20 0 20 20 20 0 Organic UV Absorbent (kg) 0.35 0.25 0.25 0.25 0.25 0.25 Inorganic UV Absorbent (kg) 0 One One One One 0 HALS (kg) 0.25 0.25 0.25 0.25 0.25 0.25 Nano-clay (kg) 0 0 One 0 One 0

ingredient:

MA functionalized HDPE resin—HDPE M 5010 from Dow, grafted with 0.25-0.40% MA in a reactive extruder;

LLDPE resin-LL 3201 manufactured by ExxonMobil;

HDPE resin-HDPE M 5010 from Dow;

Ethylene-acrylate resin-Lotryl ™ 29MA03 manufactured by Arkema;

Talc-lotalk ™ superfine manufactured by Yokal;

Organic UV absorbers—Tinuvin ™ 234 manufactured by Ciba;

Inorganic UV absorbers-SACHTLEBEN ™ Hombitec RM 130F TN from Sachtleben;

HALS-hindered amine light stabilizer from Ciba-ChimassorbTM 944;

Nano-clay-Nanomer TM I31PS manufactured by Nanocor.

Next, five polymer strips ST1-ST5 and one reference strip are prepared (ST1 contains INV1, ST2 contains INV2, etc.). All strips are made with a sheet extrusion line comprising a main single screw extruder for the core layer and a second single screw for the two outer layers. The core layer thickness is 1 mm and the outer layers each have a thickness of 0.25 mm. The outer layer and the core layer are both the same polymer composition.

evaluation

(1) Accelerated Heat Aging—The five strips are heat aged in an oven at 110 ° C. for 7 days and the relative loss of elongation at break is determined ((initial elongation − final elongation) / initial elongation).

(2) Weather resistance after heat aging-In order to simulate resistance to UV / heat aging after prolonged exposure to hot conditions, five strips were subjected to moisture / heat aging in water at 85 ° C. for 28 days to extract and hydrolyze the additives. And then exposed to artificial sunlight in a Heraeus Xenotest 1200 W WOM device. Conditions were relative humidity = 60%, black panel = 60 ° C., 102 minutes dry cycle, 18 minutes wet cycle. The relative loss of color difference (delta E) and elongation at break ((initial elongation-final elongation) / initial elongation) is measured after 10,000 hours of aging. The results are summarized in Table 5.

[Table 5] Aging test results

Strip number ST1 ST2 ST3 ST4 ST5 Reference Delta E after heat aging + weathering test 12 11 9 14 8 28 Relative loss of elongation at break after thermal aging (%) 20 22 16 18 14 40 Relative loss of elongation at break after thermal aging + weathering test (%) 28 28 29 26 26 58

From each of the six compositions, each 100 mm of 22 strips is welded with an ultrasonic horn at 20 MHz to obtain 10 pairs of test strips ST1-ST5 and a pair of Ref strips. After 48 hours of welding (called t = 0) and aging in an oven at 110 ° C. for 7 days (results call t = 7d at 110 ° C.), 5 pairs are measured (average tensile strength of welding).

Table 6 Weld Strength Resistance to Heat Aging

Strip number ST1 ST2 ST3 ST4 ST5 Reference Welding strength (N)
T = 0 1800 1650 1910 1710 1750 1380 Welding strength (N)
T = 7d at 110 ℃ 1520 1433 1800 1577 1650 825

All commercialized polymer compositions described and claimed herein and methods of making and using them can be made and performed by those skilled in the art without undue experimentation based on the knowledge of those skilled in the art in light of the present specification. Although the compositions and methods of the present invention have been described in terms of certain preferred embodiments, variations may be made in the steps of the compositions and / or methods and methods or in the order of the steps of the methods without departing from the spirit, scope, and scope of the invention. It will be apparent to one skilled in the art. It is clear that certain agents described herein may be replaced with certain chemically related agents so long as the same or similar results are obtained. Such similar substitutes or modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims. In addition, not all possible combinations of specifically described embodiments are described herein, but as will be understood by one skilled in the art, all such combinations and exchanges are within the scope of the present invention. Accordingly, all alternative combinations of each of the various elements described herein are understood to be within the scope of the present invention.

Claims (49)

A geotechnical article comprising at least one layer, wherein the at least one layer is: Thermal expansion coefficient of not more than 150 × 10 ⁻⁶ / ° C. at ambient temperature; Creep coefficient of at least 400 MPa according to ISO 899-1 at 25 ° C., 20% yield stress and 60 min load time; And At 25 ° C., having a 1 percent secant deflection coefficient of at least 700 MPa according to ASTM D790; The at least one layer is: (a) 1 to 94.5% by weight of at least one functional group-containing polymer or oligomer comprising at least one functional group per polymer or oligomer chain, wherein the at least one functional group is carboxyl, anhydride, oxirane, amino , Amido, ester, oxazoline, isocyanate or any combination thereof; (b) (i) polyamides; (Ii) polyester; (Iii) polyurethane; Or 5-98.5 wt% of at least one engineering thermoplastic selected from copolymers, block copolymers, or blends thereof; (c) optionally, from 0.5 to 94 weight percent of at least one filler; And (d) optionally, a geotechnical article formed from a composition comprising up to 93.5% by weight of an unmodified polyolefin, ethylene copolymer or ethylene terpolymer. The method according to claim 1, The filler is in the form of a powder, whisker or fiber, and when in powder form, has a mean particle size of less than 30 microns. The method according to claim 1, And (b) the content of at least one engineering thermoplastic material is from 90% by weight to 10% by weight. The method according to claim 1, (C) the at least one filler is metal oxide, metal carbonate, metal sulfate, metal phosphate, metal silicate, metal borate, metal hydroxide, silica, silicate, aluminate, alumino-silicate, chalk, talc, dolomite, Geotechnical articles comprising organic or inorganic fibers or whiskers, metals, metal-coated inorganic particles, clays, kaolins, industrial ash, concrete powders, cement, dolomite, wollastonite or combinations thereof. delete The method according to claim 1, Wherein said functional group-containing polymer or oligomer is a modified polyolefin, ethylene copolymer or ethylene terpolymer, and wherein said functional group is grafted to said polymer or oligomer. The method according to claim 1, The functional group-containing polymer or oligomer is a copolymer or terpolymer of (1) at least one unsaturated monomer and (2) at least one functional group-containing unsaturated monomer, wherein the functional group-containing unsaturated monomer is at least one unsaturated group and at least one of the Geological articles containing functional groups. The method according to claim 1, The at least one functional group containing polymer or oligomer may be a maleic anhydride grafted polyethylene, a maleic anhydride grafted ethylene-acrylic acid or methacrylic acid ester copolymer or terpolymer, a maleic anhydride grafted propylene homopolymer Or copolymers, maleic anhydride grafted ethylene-alpha olefin polymers, maleic anhydride grafted ethylene-propylene rubber, glycidyl methacrylate or acrylate (GMA) grafted polyethylene, GMA grafted ethylene Acrylic or methacrylic acid ester copolymers or terpolymers, GMA grafted propylene homopolymers or copolymers, GMA grafted ethylene-alpha olefin polymers, GMA grafted ethylene-propylene rubbers, acrylic acid or methacrylic acid grafted ethylene Copolymers or terpolymers, acrylic and methacrylic acid ionomers, styrene-maleic anhydride copolymers or terpolymers, styrene-acrylic acid or styrene-methacrylic acid copolymers or terpolymers, ethylene-glycidyl methacrylate or A geotechnical article selected from copolymers or terpolymers of ethylene-glycidyl acrylate, or any combination thereof. The method according to claim 1, The (d) unmodified polyolefin, ethylene copolymer or ethylene terpolymer may be polyethylene, ethylene-vinyl acetate, polypropylene, ethylene-alpha olefin elastomer, ethylene-propylene elastomer, ethylene-propylene diene elastomer, ethylene-acrylate ester or A geotechnical article independently selected from methacrylate ester copolymers or terpolymers, or any copolymer or combination thereof. The method according to claim 1, Wherein said composition further comprises an additive selected from a heat stabilizer, a hindered amine light stabilizer (HALS), an organic UV absorber, an inorganic UV absorber, a hydrolysis inhibitor, or a combination thereof. The method of claim 10, The hydrolysis inhibitor is reactive with end groups or side groups of the at least one engineering thermoplastic, carbodiimide, poly-carbodiimide, block isocyanates, epoxy resins, phenol resins, novolac resins, melamine resins, urea resins And a glycoluril resin, tri-isocyanuric acid and derivatives thereof, styrene-maleic anhydride resin, or at least one selected from aromatic or cycloaliphatic diacids or anhydrides thereof. The method according to claim 1, The composition further comprises nano-sized particles characterized by barrier properties, and the transmittance of the composition to molecules having molecular weight lower than 1000 Daltons, does not include nano-sized particles and the remaining composition except nano-sized particles is At least 10 percent lower in geotechnical articles compared to the same composition as said composition. The method of claim 12, The nano-size particles are nano-clay particles, nano-silica particles, nano-silicate particles, nano-alumosilicate particles, nano-zinc oxide particles, nano-titanium oxide particles, nano-zirconium oxide particles, nano-talc particles , Nano-tube particles, nano-metal particles, nano-clay flakes, nano-silica flakes, nano-silicate flakes, nano-alumosilicate flakes, nano-zinc oxide flakes, nano-titanium oxide flakes, nano-zirconium oxide flakes , Geological engineering selected from the group consisting of nano-talcum flakes, nano-tube flakes, nano-metal flakes, carbon black, nano size sulfides and sulfates and nano-size celluloses, lignin or proteins derived from plants or animals and combinations thereof article. The method according to claim 1, Wherein the article comprises an extruded or molded strip having a thickness in the range of 0.1 mm to 5 mm. The method according to claim 14, The strip having a given size, when tested by ASTM D6706-01, at a vertical stress of 4 lb / in ² (27.58 kPa) between the strip and sand, compared to the strip of the given size formed of pure MDPE or HDPE A geotechnical article having at least 10% greater traction. The method according to claim 14, A friction-promoting portion on at least one outer surface of the article, the friction-promoting portion being fabric, embossed, engraved, through-hole, finger-like extension, hair-like extension, wave-like extension, coextrusion line, combined Geotechnical articles comprising fibers or grains or aggregates, dots, mattes or combinations thereof. The method according to claim 14, The geotechnical article is a three-dimensional cellular restraint system (CCS) comprising a plurality of said strips, each strip connected in parallel with its neighbors through separate physical seams, wherein said seams are connected to each other by non-joint regions. A geotechnical article with space. 18. The method of claim 17, The three-dimensional CCS is applied to the use of blocking material, soil, rock, gravel, sand, stone, peat, clay, concrete, aggregate, and combinations thereof, use of restraint, reinforcement, or a combination thereof Geotechnical articles. 18. The method of claim 17, The seam is provided by welding, bonding, sewing, stapling, riveting or a combination thereof. The method of claim 19, And the seam is welded by at least one of ultrasonic welding, laser welding, and hot pressure welding. The method of claim 20, Geotechnical article, characterized in that at least 10% shorter welding cycle time compared to pure HDPE for the same weld dimensions. The method of claim 19, The seam is welded and the final weld strength of the two weld strips at ambient temperature is greater than 1300 N for a 100 mm weld width. The method of claim 19, The seam is welded and the final weld strength of the two weld strips at −20 ° C. is greater than 1000 N for a 100 mm weld width. The method of claim 19, The seam is welded and the final weld strength of the two weld strips at 70 ° C. is greater than 1000 N for a 100 mm weld width. 18. The method of claim 17, Wherein the distance between the seams ranges from 50 mm to 1500 mm. 18. The method of claim 17, The seam is welded and the geotechnical article maintains substantially all of the welded seam intact when the welded seam receives a continuous load of 77 kg per 100 mm weld width for 10 days at ambient temperature. . 18. The method of claim 17, The joint is welded and the geotechnical article maintains substantially all of the welded joint intact when the welded joint is subjected to a continuous load of 77 kg per 100 mm weld width for 30 days at ambient temperature. . 18. The method of claim 17, The seam is welded and the geotechnical article maintains at least 90% of the welded seam intact when the welded seam receives a continuous load of 88 kg per 100 mm weld width for 20 days at ambient temperature. . 18. The method of claim 17, The seam is welded and a geotechnical article in which at least 80% of the welded seam remains intact when the welded seam receives a continuous load of 88 kg per 100 mm weld width for 30 days at ambient temperature. . 18. The method of claim 17, The seam is welded and the geotechnical article maintains substantially all of the welded seam intact when the welded seam is subjected to a continuous load of 100 kg per 100 mm weld width for 10 days at ambient temperature. . 18. The method of claim 17, The seam is welded and a geotechnical article in which at least 80% of the welded seam remains intact when the welded seam is subjected to a continuous load of 100 kg per 100 mm weld width for 20 days at ambient temperature. . 18. The method of claim 17, Wherein the seam is welded and at least 60% of the welded seam is not damaged when the welded seam is subjected to a continuous load of 100 kg per 100 mm weld width for 30 days at ambient temperature. The method according to claim 1, A geotechnical article, further comprising a reinforcing structure adapted for use when attaching the article to a substrate. The method according to claim 1, Wherein said composition has a 1% secant modulus according to ASTM D790 of at least 600 MPa when measured at 45 ° C. The method according to claim 1, Wherein said composition has a 1% secant modulus according to ASTM D790 of at least 500 MPa when measured at 70 ° C. The method according to claim 1, Wherein the composition has a 1% secant warpage coefficient of at least 10% greater than HDPE, according to ASTM D790, when measured at a temperature of 45 ° C. The method according to claim 1, Wherein said composition has a 1% secant warpage coefficient that is at least 10% better than HDPE, according to ASTM D790, when measured at a temperature of 70 ° C. The method according to claim 1, A geotechnical article comprising at least one additional layer applied to at least one layer or coextruded or co-molded with at least one layer. The method according to claim 1, Said article is a geomembrane. The method according to claim 1, Wherein said at least one layer provides at least 10% greater thermal conductivity compared to an HDPE layer having the same dimensions. The method according to claim 1, When the at least one layer further comprises an additive selected from HALS, organic UV absorbers or inorganic UV absorbers or any combination thereof, the layer comprises at least 10 compared to HDPE layers comprising the same additives and having the same dimensions. A geotechnical article that provides a low% extraction, evaporation, hydrolysis rate, or combination thereof. The method according to claim 1, Wherein said at least one layer exhibits at least 10% lower weight gain compared to an HDPE layer having the same dimensions after immersion in n-octane at 60 ° C. for 60 days. The method according to claim 1, Wherein said at least one layer exhibits a retention of at least 10% superior elongation at break as compared to PET layers having the same dimensions after immersion in an aqueous solution of pH = 11 for 60 days at 45 ° C. The method according to claim 1, Said at least one layer exhibiting a retention of at least 10% superior elongation at break as compared to a PA6 layer having the same dimensions after immersion in an aqueous solution of pH = 4 for 60 days at 45 ° C. The method according to claim 1, The composition comprises a continuous phase and discontinuous phase dispersed throughout the continuous phase, wherein substantially all of the region has a largest dimension of 10 microns or less. The method according to claim 1, Wherein the geotechnical article is a cellular restraint system, geomembrane or geogrid. A method of making a geotechnical article comprising at least one layer, wherein the at least one layer is: Thermal expansion coefficient of less than 150 ppm / ° C at ambient temperature; Resistance to acidic media larger than polyamide 6 resin or to basic media larger than PET resin, or both; Resistance to hydrocarbons greater than HDPE; Creep coefficient of at least 400 MPa according to ISO 899-1 at 25 ° C., 20% yield stress and 60 min load time; And At 25 ° C., having a 1 percent secant deflection coefficient of at least 700 MPa according to ASTM D790; The at least one layer is: (a) 1 to 94.5% by weight of at least one functional group-containing polymer or oligomer comprising at least one functional group per molecule, wherein the at least one functional group is carboxyl, anhydride, oxirane, amino, amido , Esters, oxazolines, isocyanates or any combination thereof; (b) (i) polyamides; (Ii) polyester; (Iii) polyurethane; Or 5 to 98.5 weight percent of at least one engineering thermoplastic selected from copolymers, block copolymers, or blends thereof; (c) optionally, from 0.5 to 94 weight percent of at least one filler; And (d) optionally, a composition comprising up to 93.5% by weight of an unmodified polyolefin, ethylene copolymer or ethylene terpolymer; The method is: (i) providing (a) at least one functional group-containing polymer or oligomer and (b) at least one engineering thermoplastic; (Ii) melt kneading the combined (a) and (b); (Iii) adding at least one filler (c) and further melt kneading the combined (a), (b) and (c); (iv) optionally adding (d) at least one unmodified polyolefin, ethylene copolymer or ethylene terpolymer to any one of (a), (b) or (c) or a combination thereof; And (v) extruding the composition into a strip, profile, film or sheet, powder, or a plurality of beads, flakes, granules or pellets. The method of claim 47, Re-melting the powder or the plurality of beads, flakes, granules or pellets and extruding, forming or forming the remelt obtained in the remelting into strips, profiles, films, sheets or shaped three-dimensional geological articles Further comprising the step of: The method of claim 47, The geotechnical article is a cellular restraint system, geomembrane or geogrid.

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