WO1997011114A9 - Compositions polymeres ayant une haute teneur en charge - Google Patents

Compositions polymeres ayant une haute teneur en charge

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Publication number
WO1997011114A9
WO1997011114A9 PCT/US1996/015018 US9615018W WO9711114A9 WO 1997011114 A9 WO1997011114 A9 WO 1997011114A9 US 9615018 W US9615018 W US 9615018W WO 9711114 A9 WO9711114 A9 WO 9711114A9
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WO
WIPO (PCT)
Prior art keywords
weight
amount
substituted
filled
composition
Prior art date
Application number
PCT/US1996/015018
Other languages
English (en)
Other versions
WO1997011114A1 (fr
Filing date
Publication date
Application filed filed Critical
Priority to AU70760/96A priority Critical patent/AU7076096A/en
Publication of WO1997011114A1 publication Critical patent/WO1997011114A1/fr
Publication of WO1997011114A9 publication Critical patent/WO1997011114A9/fr

Links

Definitions

  • the invention relates generally to extender-filled thermoplastic compositions. More particularly, the invention relates to polyethylene compositions that can be highly loaded with low cost fillers, while maintaining enough flexibility for many critical applications.
  • thermoplastic materials have increased not so much through development of new polymers, but through modification of existing ones.
  • properties of polymeric compositions such as strength, resistance to UV and chemical oxidation, shielding, electrical conductivity, and cost can be modified.
  • extender fillers some inexpensive added extender fillers (hereinafter referred to as "extenders”) increase the strength of the polymeric product and decrease its cost. All too often, however, while the targeted properties improve, some other properties deteriorate beyond the level acceptable for the given application.
  • Kiingaman and Ehrenreich, Pyroplastoid Particles, Composition and Method of Production discloses a method for separating filler particles from coal-burning power plants' fly ash for use in a nylon-based composition.
  • These pyroplastoid particles are ellipsoidal in shape and at least 90 % by weight are less than 25 ⁇ in size.
  • various so-called “coupling agents” are empirically selected, and fillers are treated with them either prior to being mixed into the composition, or during in- line compounding.
  • fillers are treated with them either prior to being mixed into the composition, or during in- line compounding.
  • silicone hydrates S n H2n+2
  • preliminary treatment of a filler with the hydrates of Si or Ti will improve the impact strength, thermal resistance, water stability, and strain-stress properties of filled compositions.
  • Atactic polypropylene has been known to increase the levels of carbon black and fire retardants in compositions, Kawai et al., Electroconductive Resin Composition, U.S. Pat. No. 4,425,262 (10 January 1984) and Atwell et al., Flame Retardant Hot Melt Adhesive Compositions Using Brominated Styrene/Atactic Polypropylene Graft Copolymers, U.S. Pat. No. 5,041 ,484 ( 20 August 1991 ). Atactic polypropylene has also been used as a thermally- removable binding agent for ceramics, Dolhert, Clean Burning Green Ceramic Tape Cast System Using Atactic Polypropylene Binder, U.S. Pat. No. 5,256,609 (26 October 1993). However, these compositions are not suitable for molding into rigid components that maintain some flexibility.
  • extender fillers improve the modulus of elasticity of a composition, they drastically reduce its elongation at its breaking point. For any product which incorporates flexing elements or which has to withstand even occasional surface impacts, such as containers, furniture, instrument housings, automotive oil pans, bumpers and body panels, this reduced elongation is detrimental. Thus, for all practical purposes these filled polymers cannot be effectively used for items requiring stretching or bending properties.
  • Table 1 shows the change of some properties for a selected group of polymer compositions loaded about 40 wt. % with various microspheric fillers.
  • these microspheric fillers improve the modulus of elasticity of a composition, but drastically reduce its elongation at the break.
  • these filled polymers cannot be effectively used for critical items under stretch or bending.
  • This invention relates to extender-filled and atactic polypropylene-treated polymer compositions which, at high levels of loading (30 % by weight and higher), retain sufficient base material elasticity as well as the strength required for many critical applications.
  • the compositions of the invention are formed mostly of HDPE, LDPE and LLDPE, filled with atactic polypropylene-treated fly ash.
  • the base material may also include recycled polymeric materials.
  • the APP-treating permits the composition of the invention to be filled with up to 80% by weight of filler, while retaining its flexibility.
  • the highly-filled composition is extruded into pipes, sheets, construction elements or general purpose, collapsible shipping boxes.
  • compositions of the invention have increased UV and thermal stability, a smaller coefficient of thermal expansion, and higher resistance to chemical substances and sea water than the prior art compositions, while having a higher productivity.
  • polyvinyl chloride PVC
  • polyethylene theraphthalate PET
  • atactic polypropylene- treated fly ash 30 wt. % and higher.
  • calcium carbonate is used as an extender.
  • Fig. 1 a is a graph showing experimental results for Maximum Elongation at Yield vs. APP/Ash Ratio for 30 wt. % ash-filled HDPE/LLDPE (70/30) compositions, shown in continuous line, and HDPE/LDPE (70/30) compositions, show in dashed line, for various APP concentrations;
  • Fig. 1 b is a graph showing experimental results for Tensile Strength vs. APP/Ash Ratio for 30 wt. % ash-filled HDPE/LLDPE (70/30) compositions, shown in continuous line, and HDPE/LDPE (70/30) compositions, show in dashed line, for various APP concentrations;
  • Fig. 1c is a graph showing experimental results for Moment of Rotation vs. APP/Ash Ratio for 30 wt. % ash-filled HDPE/LLDPE (70/30) compositions, shown in continuous line, and HDPE/LDPE (70/30) compositions, show in dashed line, for various APP concentrations;
  • Fig. 1d is a graph showing experimental results for Productivity vs. APP/Ash Ratio for 30 wt. % ash-filled HDPE/LLDPE (70/30) compositions, shown in continuous line, and HDPE/LDPE (70/30) compositions, show in dashed line, for various APP concentrations; and
  • Fig. 2 is a graph showing the distribution of the fly ash particles used in the examples of the composition of the invention, where dashed line shows distribution of the particles, and continuous line the cumulative distribution.
  • fly ash is an ample byproduct of the energy generation process. For all practical purposes, fly ash is inexhaustible source as a low cost extender filler for plastic compositions: in 1993, 60M tons of it were produced in the US, and only 21% used for any useful purpose; the rest of the fly ash was deposited to landfills at the cost of $40 to $60/ton for their producers.
  • fly ash When pulverized coal is blown into a high temperature furnace and burned, a byproduct of this process melts into hollow particles resembling microspheres (cenospheres). A large percentage of these particles are hollow because the melt settles around rising gas bubbles. These particles are drawn into the exhaust system and, before they can enter into the atmosphere, are collected by various anti-pollution devices, such as cyclones and baghouses.
  • the chemical composition of fly ash depends on the coal which is burned, on the temperature and on other aspects of the burning process. Currently, fly ash has little commercial use. Although some fly ash is used as a filler for concrete, and as an occasional soil additive in agriculture, much of the produced fly ash is disposed in landfills at the expense of the producers.
  • the preferred embodiment of the invention uses atactic polypropylene at- [CH2CH(CH3)]n of 0.83 to 0.87 g/cm 3 specific weight (hereinafter referred to as APP).
  • APP improves the quality of bond between the filler and the rest of the polymer composition which, in turn, helps provide for even highly filled compositions to retain much of the base material's elongation.
  • the best amounts of the modifying agent, APP were evaluated experimentally. In these experiments, two different base materials for compositions were investigated: (a) various blends of HDPE with LDPE, and (b) various blends of HDPE with LLDPE. During these studies, the following relationships were varied and the outcomes compared:
  • the amount of fly ash in the composition was changed from 30 to 80 wt. % of the entire composition;
  • the amount of the APP was changed from about 0.1 to 15 wt. % of the composition.
  • Table 2 contains experimental results for 30 wt. % fly ash-filled HDPE/LDPE (70/30) and HDPE/LLDPE (70/30) compositions for various APP concentrations.
  • compositions correspond with Examples 1 and 2, respectively.
  • Figs. 1 a - d are graphs of the results listed in Table 2.
  • Table 3 is a table listing the properties of 30 wt. % ash-filled, APP-treated HDPE/LDPE (70/30 wt.) composition, according to the preferred embodiment of the invention. -8-
  • Creep modules EQ 1 ,100 MPa (-157,000 PSI)
  • Table 4 is a table listing the properties of 30 wt. % ash-filled HDPE/LDPE (90/10) and HDPE/LLDPE (90/10) compositions for various APP concentrations.
  • Base Polymer Base Polymer: Base Polymer:
  • control samples were made for comparison using prior art coupling agents, such as calcium stearate and vinyltriethoxy saline. All other conditions were kept the same.
  • test samples show that, starting above a 10 wt. % level of filling, all the test samples became unstretchable, for all practical purposes.
  • the test samples break before forming a distinctive neck.
  • the fly ash was treated with APP at certain APP/Ash ratios, the tested samples retained up to 70% or even 90% of the base material's cold stretching ability even at 30-35 wt. % loading.
  • the upper level of APP/Filler ratio can go as high as 10 wt. %.
  • the upper level of APP/Filler can be as high as 15%.
  • filled compositions usually lose some of the base material's thermal resistance, the filled compositions treated with APP, especially those filled with fly ash, become more resistant to thermooxidative degradation than the initial base material.
  • the fly ash used in the experimental work had the following properties
  • the curve was obtained using a device based on Coulter Counter measuring technique. This distribution curve shows that the particles of the fly ash used had the mean about 12 mm, 85% of particles were less than 20 mm, with as little as possible of dust-like fractions (1 mm and less). -12-
  • the polymeric components, fillers and APP were blended in M-2400/K two-step mixer (300-330 kg/hour capacity, made by MTI, Germany); hot mixing for 20 to 25 minutes at 90°C, and then cold mixing for 10 to 20 mtnutes at 40°C The primary purpose of the second stage was cooling.
  • the pipe had excellent surface and the following properties:
  • thermooxidation tests showed that under the conditions specified in Table 10 the invented composition has almost 50% higher resistance to thermal oxidation than HDPE.
  • Example 1 The only difference with Example 1 was that instead of LDPE LLDPE was used in the base material.
  • the pipe had excellent surface and the following properties:
  • Example 2 The same composition as in Example 2 was prepared and extruded into a narrow sheet. From this narrow sheet, standard double-bell test specimens were stamped out and tested on Instron test equipment. The speed of deformation was 50 mm/min. Under such stretch, the test specimens developed well observed necks: the maximum coefficient of cold stretch exceeded 6 before the specimens broke.
  • a 500 mm diameter and 300 ⁇ m wall thickness sleeve was produced on a blow extruder.
  • the sleeve had the following properties:
  • the sleeve was cut into meter-long pieces. Each piece was thermo-welded in such a way that it formed a flexible, waterbed mattress-like solar collector, having 12 passages for heated water, an incoming manifold and an outgoing manifold. These solar collectors were tested for three years in a region which had monthly average solar radiation of approximately 36 MJ/m 2 . On a sunny day, this less than 0.7 m 2 solar collector, when in horizontal position and uncovered, heated 45 liters of water hourly from 20°C to 45°C.
  • the sheets also had excellent surface, strong weld, and improved rheology leading to higher productivity than extruding the same sheet from unfilled HDPE. -18-
  • This composition can be used for products which should not collect static electricity, such as conveyor belts and various ventilation pipes in mines and chemical plants, and radiators for automobiles.
  • Polyurethane foam 80 wt. (polyurethane foam was recaptured from waste stream)
  • HPDE cycled 50 wt (was recaptured from waste stream as milk and water bottles)
  • composition was extruded into 50 mm x 4 mm pipe.
  • the pipe was tested for its maximum deformation under a load of 1 ,000 Newton acting perpendicular to its wall; the surface of contact was 25 cm 2 . That load caused less than a 10% change in diameter.
  • Such a pipe can be laid into concrete. -20-
  • Example 4 The same composition as in Example 4 was prepared, and two different sizes of hoses were extruded from this composition:
  • OD 100 mm
  • wall thickness 200 ⁇ m
  • HDPE (recycled) 38 wt.
  • a 100 ⁇ m film was extruded from it.
  • composition A consisted of fresh HDPE and fresh LDPE:
  • Composition B is a composition of Composition B:
  • a 1.5 mm thick and 1 ,500 mm wide sheet was coextruded from these two compositions.
  • Two outside layers of the sheet were coextruded from composition A, and the middle layer from composition B.
  • the outside and inside layers were both 50 ⁇ m thick, the middle layer was 1.4 mm thick. This sheet had excellent resistance to the elements.
  • Example 13 The outside layers were the same as Example 13, but a different composition B was used for the middle layer.
  • Recycled polyethylene therephthalate (PET) was used instead of HDPE/LDPE, and the proportions of the composition were different:
  • Example 13 a 1.5 mm thick and 1 ,500 mm wide sheet was coextruded from these two compositions.
  • Two outside layers of the sheet were coextruded from composition A, and the middle layer from composition B.
  • the outside and inside layers were both 50 ⁇ m thick, the middle layer was 1.4 mm thick.
  • This sheet had also excellent resistance to the elements.
  • the composition was extruder to insulate about 1 mm 2 copper wire; the insulation was about 300 ⁇ m thick. The insulation displayed good adhesion to the wire and good resistance to the elements.
  • the strip was welded with a strip made of HDPE, and another strip made of PVC.
  • the welds were excellent.
  • the composition was used for anti-corrosion coating of 100 mm metal pipes.
  • the composition was loaded into a hopper of plasma deposition equipment and deposited as a 250 ⁇ m to 300 ⁇ m thick coating. During the plasma-deposition, the surface temperature of the pipes was kept over 150°C; -25-
  • the equipment used for plasma deposition was that widely applied in anti- corrosive coating of pipe.

Abstract

Les compositions de polymères à haute teneur en charges de l'invention conservent une proportion suffisante de l'élasticité du matériau de base et de sa résistance mécanique, nécessaires pour beaucoup d'applications critiques. Les compositions de l'invention sont constituées de polyéthylène haute densité, de polyéthylène basse densité et de polyéthylène basse densité linéaire, contenant une charge traitée par du polypropylène atactique. Ces compositions sont utilisées pour réaliser par extrusion des tubes ou des plaques. Le traitement par le polypropylène atactique permet aux compositions de l'invention de recevoir jusqu'à 80 % de charge, tout en restant flexibles. Les compositions à haute teneur en charge de l'invention ont une durabilité accrue, leur plage de températures d'utilisation est plus large, leur compatibilité avec d'autres matériaux thermoplastiques est améliorée dans les opérations de soudage, de co-injection et de co-extrusion, et elles sont moins chères à produire que les compositions de la technique antérieure.
PCT/US1996/015018 1995-09-20 1996-09-17 Compositions polymeres ayant une haute teneur en charge WO1997011114A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU70760/96A AU7076096A (en) 1995-09-20 1996-09-17 Highly-filled polymer compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53145895A 1995-09-20 1995-09-20
US08/531,458 1995-09-20

Publications (2)

Publication Number Publication Date
WO1997011114A1 WO1997011114A1 (fr) 1997-03-27
WO1997011114A9 true WO1997011114A9 (fr) 1997-06-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (2)

Country Link
AU (1) AU7076096A (fr)
WO (1) WO1997011114A1 (fr)

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US7211206B2 (en) 2004-01-23 2007-05-01 Century-Board Usa Llc Continuous forming system utilizing up to six endless belts
US7763341B2 (en) 2004-01-23 2010-07-27 Century-Board Usa, Llc Filled polymer composite and synthetic building material compositions
AU2005267399A1 (en) 2004-06-24 2006-02-02 Century-Board Usa, Llc Continuous forming apparatus for three-dimensional foamed products
US20060100466A1 (en) 2004-11-08 2006-05-11 Holmes Steven A Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same
US20070222105A1 (en) 2006-03-24 2007-09-27 Century-Board Usa, Llc Extrusion of polyurethane composite materials
US20090308009A1 (en) * 2008-06-11 2009-12-17 Boor Billibob J Composite Material Roofing Structure
US9481759B2 (en) 2009-08-14 2016-11-01 Boral Ip Holdings Llc Polyurethanes derived from highly reactive reactants and coal ash
US8846776B2 (en) 2009-08-14 2014-09-30 Boral Ip Holdings Llc Filled polyurethane composites and methods of making same
WO2013052732A1 (fr) 2011-10-07 2013-04-11 Boral Industries Inc. Composites de polymère inorganique/polymère organique et procédés pour les préparer
ITMI20130557A1 (it) 2013-04-09 2014-10-10 Piaggio & C Spa Miscela poliolefinica migliorata
WO2014168633A1 (fr) 2013-04-12 2014-10-16 Boral Ip Holdings (Australia) Pty Limited Composites formés à partir d'une charge absorbante et d'un polyuréthane
US10138341B2 (en) 2014-07-28 2018-11-27 Boral Ip Holdings (Australia) Pty Limited Use of evaporative coolants to manufacture filled polyurethane composites
WO2016022103A1 (fr) 2014-08-05 2016-02-11 Amitabha Kumar Composites polymères chargés comprenant des fibres de courte longueur
WO2016118141A1 (fr) 2015-01-22 2016-07-28 Boral Ip Holdings (Australia) Pty Limited Composites de polyuréthanne hautement chargés
CN104829972A (zh) * 2015-05-15 2015-08-12 六盘水康博木塑科技有限公司 粉煤灰装饰墙板及其制备方法
WO2016195717A1 (fr) 2015-06-05 2016-12-08 Boral Ip Holdings (Australia) Pty Limited Composites de polyuréthane chargés à charges légères
KR20180018723A (ko) 2015-06-15 2018-02-21 이메리즈 미네랄즈 리미티드 사출 성형을 위한 조성물
CN105348564B (zh) * 2015-10-30 2018-06-26 太原理工大学 一种低密度复合白卡纸专用无机粉体的制备方法
US20170267585A1 (en) 2015-11-12 2017-09-21 Amitabha Kumar Filled polyurethane composites with size-graded fillers
WO2017147465A1 (fr) 2016-02-25 2017-08-31 Interfacial Consultants Llc Concentrés polymères hautement chargés
CN106674817A (zh) * 2016-12-29 2017-05-17 六盘水康博木塑科技有限公司 一种粉煤灰生态板及其制作方法

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