Singlelayer and multilayer polyolefin foam pipes
Abstract
Single-layer or multi-layer polyolefin foam tube with improved compressive strength, where at least one of the layers consists of a polyolefin foam layer, characterized in that the polyolefin foam layer, which has a density of 50 to 850 kg / m3, includes mixtures of: A) 5 to 80% by weight of a compound A, selected from modified propylene polymers with a melt index of 0.05 to 10 g / 10 min at 230 ° C / 2.16 kg, preferably 0.2 to 10 g / 10 min at 230 ° C / 2, 16 kg, whose modified propylene polymers exhibit a cold strain hardening behavior, and mixtures of such modified propylene polymers, B) 20 to 95% by weight of a compound B, selected from propylene homopolymers with a stereospecificity index> 98% and a melt index of 0.05 to 10 g / 10 min at 230 ° C / 2.16 kg, preferably from 0.1 to 10 g / 10 min at 230 ° C / 2, 16 kg and copolymers of 80 to 99.9% by weight of propylene and 0.1 to 20% by weight of ethylene or alpha-olefins with 4 to 18 carbon atoms with a stereospecificity index of the homopolymer matrix of propylene of> 96% and a melt index of 0.1 to 10 g / 10 min at 230 ° C / 2, 16 kg, and mixtures of such homopolymers and / or copolymers of propylene, and C) optionally, the usual amounts of stabilizers and / or processing aids and / or antistatics and / or pigments and / or nucleating agents and / or fillers as auxiliary substances.

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Projected expiry passed 10 July 2021, 5.2 years ago.
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17 claims: 13 independent, 4 dependent
- 1ES 2 219 559 T3 REIVINDICACIONES 1. Tubo de espuma poliolefínica de una sola capa o de múltiples capas con una resistencia mejorada a la compresión, en donde al menos una de las capas está constituida por una capa de espuma poliolefínica, caracterizado porque la capa de espuma poliolefínica, que tiene una densidad de 50 a 850 kg/m 3 , comprende mezclas de:A) 5 a 80% en peso de un compuesto A, seleccionado entre polímeros de propileno modificados con un índice de fusión de 0,05 a 10 g/10 min a 230°C/2,16 kg, preferentemente de 0,2 a 10 g/10 min a 230°C/2,16 kg, cuyos polímeros de propileno modificados presentan un comportamiento de endurecimiento por deformación en frío, y mezclas de tales polímeros de propileno modificados, B) 20 a 95% en peso de un compuesto B, seleccionado entre homopolímeros de propileno con un índice de estereoespecificidad 98% y un índice de fusión de 0,05 a 10 g/10 min a 230°C/2,16 kg, preferentemente de 0,1 a 10 g/10 min a 230°C/2,16 kg y copolímeros de 80 a 99,9% en peso de propileno y 0,1 a 20% en peso de etileno o alfa-olefinas con 4 a 18 átomos de carbono con un índice de estereoespecificidad de la matriz de homopolímero de propileno de 96% y un índice de fusión de 0,1 a 10 g/10 min a 230°C/2,16 kg, y mezclas de tales homopolímeros y/o copolímeros de propileno, y C) opcionalmente, las cantidades usuales de estabilizantes y/o auxiliares de procesado y/o antiestáticos y/o pigmentos y/o agentes nucleantes y/o cargas como sustancias auxiliares.
- 2Tubo de espuma poliolefínica según la reivindicación 1, caracterizado porque la capa de espuma poliolefínica, que tiene una densidad de 150 a 850 kg/m 3 , comprende mezclas de 5 a 50% en peso de compuesto A y de 50 a 95% en peso de compuesto B.
- 3Tubo de espuma poliolefínica según cualquiera de las reivindicaciones 1 ó 2, caracterizado porque la capa de espuma poliolefínica comprende mezclas que contienen hasta 3% en peso, basado en la suma de los polímeros de propileno, de agentes α-nucleantes.
- 4Tubode espuma poliolefínica según cualquiera de las reivindicaciones 1 a3, caracterizado porque los polímeros de propileno modificados A) se preparan mediante:a) mezcla de un polímero de propileno sin modificar en partículas, que comprende: a1) homopolímeros de propileno, en especial homopolímeros de propileno con un peso molecular medio en peso MW de 500.000 a 1.500.000 g/mol, y/o a2) copolímeros de propileno y etileno y/o α-olefinas con 4 a 18 átomos de carbono, o de mezclas de tales copolímeros, con 0,05 a 3% en peso, basado en la composición de poliolefina utilizada, de peróxidos de acilo, peróxidos de alquilo, hidroperóxidos, perésteres y/o peroxicarbonatos como generadores de radicales libres capaces de descomponerse térmicamente, si se desea diluidos con disolventes inertes, con calentamiento a 30100°C, preferentemente a 60-90°C, b) sorción de monómeros bifuncionales volátiles por el polímero de propileno en partículas a partir de la fase gaseosa a una temperatura T (°C) de 20 a 120°C, preferentemente 60 a 100°C, en donde la cantidad de los monómeros bifuncionalmente insaturados absorbidos es de 0,01 a 10% en peso, preferentemente de 0,05 a 2% en peso, basado en el polímero de propileno utilizado, y luego c) calentamiento y fusión de la composición poliolefínica en partículas en una atmósfera que comprende un gas inerte y/o los monómeros bifuncionales volátiles, desde la temperatura de sorción a 200°C, tras lo cual se descomponen los generadores de radicales libres capaces de descomponerse térmicamente y luego d) calentamiento de la masa fundida a una temperatura de hasta 280°C con el fin de separar los monómeros sin reaccionar y los productos de descomposición, e) aglomeración de la masa fundida de manera conocida per se.
- 5Tubo de espuma poliolefínica según cualquiera de las reivindicaciones 1 a 4, caracterizado porque los polímeros del compuesto B se obtienen mediante polimerización con un sistema catalítico Ziegler-Natta que comprende componentes sólidos conteniendo titanio, un compuesto de organoaluminio como cocatalizador y un donador externo que tiene la fórmula general R x R' y Si(RO)4-x- y ES 2 219 559 T3 en donde R, R' y R” son idénticos o diferentes y representan residuos de hidrocarburos alifáticos o aromáticos, ramificados o cíclicos, eyyxindependientementeentresíson0ó1, siempre que x+y sea 1 ó2.
- 6Tubo de espuma poliolefínica según la reivindicación 5, caracterizado porque el donador externo es diciclopentildimetoxisilano.
- 7Tubo de espuma poliolefínica según cualquiera de las reivindicaciones 1 a 6, caracterizado porque la capa de espuma poliolefínica comprende mezclas de 20 a 50% en peso de compuesto A con índices de fusión de 0,3 a 4 g/10 min a 230°C/2,16 kg y 50 a 80% en peso del compuesto B con índices de estereoespecificidad de la matriz de polipropileno del orden de 97 a 99% e índices de fusión del orden de 0,1 a 2 g/10 min a 230°C/2,16 kg, en donde el compuesto B está constituido esencialmente por copolímeros en bloque de propileno.
- 8Tubo de espuma poliolefínica según cualquiera de las reivindicaciones 1 a 7, en donde el tubo de poliolefina es un tubo de una sola capa, caracterizado porque la única capa está constituida por una capa de espuma poliolefínica que comprende mezclas de 20 a 80% en peso de compuesto A con índices de fusión de 0,3 a 4 g/10 min a 230°C/2,16 kg y 20 a 80% en peso de compuesto B con índices de estereoespecificidad de la matriz de polipropileno del orden de 98 a 99% e índices de fusión del orden de 0,1 a 2 g/10 min a 230°C/2,16 kg, en donde dicha capa de espuma tiene una densidad de 100 a 850 kg/m 3 .
- 9Tubo de espuma poliolefínica según la reivindicación 8, caracterizado porque la capa de espuma poliolefínica tiene una densidad de 150 a 700 kg/m 3 , preferentemente de 250 a 400 kg/m 3 .
- 10Tubo de espuma poliolefínica según cualquiera de las reivindicaciones 1 a 7, en donde el tubo de poliolefina es un tubo de múltiples capas, caracterizado porque el tubo de espuma poliolefínica de múltiples capas es un tubo de acero revestido con poliolefina con una capa interior de acero, una capa intermedia de espuma de poliolefina y una capa exterior de polímero sin espumar.
- 11Tubo de espuma poliolefínica según cualquiera de las reivindicaciones 1 a 7, caracterizado porque la capa de espuma poliolefínica tiene una densidad de 400-850 kg/m 3 , preferentemente de 500-850 kg/m 3 , prefiriéndose en especial una densidad de 550-800 kg/m 3 .
- 12Tubo de espuma poliolefínica según cualquiera de las reivindicaciones 1 a 7, en donde el tubo de poliolefina es un tubo de dos capas, caracterizado porque la primera capa comprende una capa de polipropileno sin espumar y la segunda capa comprende la capa de espuma poliolefínica.
- 13Tubo de espuma poliolefínica según cualquiera de las reivindicaciones 1 a 7, en donde el tubo de poliolefina es un tubo de múltiples capas, caracterizado porque el tubo de espuma poliolefínica de múltiples capas está constituido por una capa interior de polipropileno sin espumar, una capa intermedia de espuma poliolefínica y una capa exterior de polipropileno sin espumar.
- 14Un procedimiento para la producción de tubos de acero revestidos con espuma poliolefínica que presentan una resistencia mejorada a la compresión, que comprenden un núcleo de tubo de acero, una capa intermedia de espuma de poliolefina y una capa exterior de polímero sin espumar, mediante la tecnología de revestimiento de tubos de acero mediante extrusión/rotación o mediante la tecnología del revestimiento de tubos con boquilla de cruceta, caracterizado porque la capa de espuma poliolefínica tiene una densidad de 400 a 850 kg/m 3 y las poliolefinas usadas en el revestimiento de espuma son mezclas de:A) 5 a 80% en peso de un compuesto A, seleccionado entre polímeros de propileno modificados con un índice de fusión de 0,05 a 10 g/10 min a 230°C/2,16 kg, preferentemente de 0,2 a 10 g/10 min a 230°C/2,16 kg, cuyos polímeros de propileno modificados presentan un comportamiento de endurecimiento por deformación en frío, y mezclas de tales polímeros de propileno modificados, B) 20 a 95% en peso de un compuesto B, seleccionado entre homopolímeros de propileno con un índice de estereoespecificidad 98% y un índice de fusión de 0,05 a 10 g/10 min a 230°C/2,16 kg, preferentemente de 0,1 a 10 g/10 min a 230°C/2,16 kg y copolímeros de 80 a 99,9% en peso de propileno y 0,1 a 20% en peso de etileno o alfa-olefinas con 4 a 18 átomos de carbono con un índice de estereoespecificidad de la matriz de homopolímero de propileno de 96% y un índice de fusión de 0,1 a 10 g/10 min a 230°C/2,16 kg, y mezclas de tales homopolímeros y/o copolímeros de propileno, y C) opcionalmente, las cantidades usuales de estabilizantes y/o auxiliares de procesado y/o antiestáticos y/o pigmentos y/o agentes nucleantes y/o cargas como sustancias auxiliares, en donde la masa fundida de dichas mezclas en el proceso de revestimiento con espuma del tubo de acero contiene hasta 12% en peso, basado en la mezcla poliolefínica, de agentes expansionantes químicos que desprenden gas, o hidrocarburos, hidrocarburos halogenados y/o gases como agentes expansionantes y en donde los tubos de acero se precalientan a una temperatura comprendida preferentemente entre 170 y 230°C y la extrusora del revestimiento de espuma presenta un perfil de temperatura que va preferentemente desde 175 a 250°C. ES 2 219 559 T3
- 15Un procedimiento para la producción de tubos de material plástico de espuma poliolefínica con una resistencia mejorada a la compresión mediante coextrusión o moldeo por inyección o moldeo por soplado, en donde al menos una de las capas está constituida por una capa de espuma poliolefínica, en donde la capa de espuma poliolefínica tiene una densidad de 50 a 850 kg/m 3 y las poliolefinas usadas para la capa de poliolefina espumada son mezclas de:A) 5 a 80% en peso de un compuesto A, seleccionado entre polímeros de propileno modificados con un índice de fusión de 0,05 a 10 g/10 min a 230°C/2,16 kg, preferentemente de 0,2 a 10 g/10 min a 230°C/2,16 kg, cuyos polímeros de propileno modificados presentan un comportamiento de endurecimiento por deformación en frío, y mezclas de tales polímeros de propileno modificados, B) 20 a 95% en peso de un compuesto B, seleccionado entre homopolímeros de propileno con un índice de estereoespecificidad 98% y un índice de fusión de 0,05 a 10 g/10 min a 230°C/2,16 kg, preferentemente de 0,1 a 10 g/10 min a 230°C/2,16 kg y copolímeros de 80 a 99,9% en peso de propileno y 0,1 a 20% en peso de etileno o alfa-olefinas con 4 a 18 átomos de carbono con un índice de estereoespecificidad de la matriz de homopolímero de propileno de 96% y un índice de fusión de 0,1 a 10 g/10 min a 230°C/2,16 kg, y mezclas de tales homopolímeros y/o copolímeros de propileno, y C) opcionalmente, las cantidades usuales de estabilizantes y/o auxiliares de procesado y/o antiestáticos y/o pigmentos y/o agentes nucleantes y/o cargas como sustancias auxiliares, en donde la masa fundida de dichas mezclas en el proceso de espumado por coextrusión o moldeo por inyección o moldeo por soplado contiene hasta 12% en peso, basado en la mezcla poliolefínica, de agentes expansionantes químicos que desprenden gas, o hidrocarburos, hidrocarburos halogenados y/o gases como agentes expansionantes.
- 16Uso de tubos de espuma poliolefínica obtenibles mediante el procedimiento según la reivindicación 15, caracterizado porque se abren mediante corte los tubos de espuma poliolefínica antes de su aplastamiento y opcionalmente se enrollan las láminas de espuma poliolefínica de múltiples capas resultantes.
- 17Uso de los tubos de espuma poliolefínica según cualquiera de las reivindicaciones 1 a 13 como tubos de acero revestidos para el transporte de productos de crudo o gas de petróleo o para aplicaciones de calefacción en ciudades;como tubos de una sola capa para fines aislantes y para aplicaciones carentes de presión o de baja presión;y como tubos poliolefínicos de múltiples capas para el transporte de fluidos calientes o fríos.
Independent claims17
117 paragraphs in 6 sections, as filed
ES 2 219 559 T3
DESCRIPTION
Single-layer and multi-layer polyolefin foam tubes.
The invention relates to single-layer and multi-layer polyolefin foam tubes with improved compressive strength from a mixture of propylene polymers, as well as a process for their production.
Polyolefinic foam materials are already known from propylene polymers (US-A-5,527,573) or from mixtures of propylene polymers and ethylene copolymers (EP-A-0 291 764) or polyethylene (GB-A- 2,099,431). Known modified polypropylenes, which are suitable for the production of extrusion foams, are silane grafted propylene polymers (EP-A-0 646 622) or propylene polymers modified by high energy electron radiation (EP-A-0 190 889).
Multilayer plastic tubes are also known, comprising a base tube made of propylene polymers (WO 98/43806; WO 97/33116) or coatings of steel tubes with a layer of propylene polymer (DE-A- 198 15 046).
The drawback of these known tubes of multilayer plastic material is their high coefficient of thermal conductivity. On the other hand, known propylene polymer foam materials have a low compressive strength which is insufficient for certain applications.
The object of the present invention is to provide single-layer and multi-layer polyolefin foam tubes with improved resistance to compression, wherein at least one of the layers consists of a layer of polyolefin foam, the tubes of which avoid the drawbacks of known products.
According to the present invention, this object is achieved by means of a layer of polyolefinic foam, which has a density of 50 to 850 kg / m<sup>3</sup> , comprising mixtures of
A) 5 to 80% by weight of a compound A, selected from modified propylene polymers with a melting index of 0.05 to 10 g / 10 min at 230 ° C / 2.16 kg, preferably 0.2 to 10 g / 10 min at 230 ° C / 2.16 kg, whose modified propylene polymers exhibit cold strain hardening behavior, and mixtures of such modified propylene polymers,
B) 20 to 95% by weight of a compound B, selected from propylene homopolymers with a stereospecificity index> 98% and a melting index of 0.05 to 10 g / 10 min at 230 ° C / 2.16 kg , preferably 0.1 to 10 g / 10 min at 230 ° C / 2.16 kg and copolymers of 80 to 99.9% by weight of propylene and 0.1 to 20% by weight of ethylene or alpha-olefins with 4 at 18 carbon atoms with a stereospecificity index of the propylene homopolymer matrix of> 96% and a melt index of 0.1 to 10 g / 10 min at 230 ° C / 2.16 kg, and mixtures of such propylene homopolymers and / or copolymers, and
C) optionally, the usual amounts of stabilizers and / or processing aids and / or antistatics and / or pigments and / or nucleating agents and / or fillers as auxiliary substances.
Tubes having a polyolefinic foam layer according to the present invention show improved compressive strength compared to conventional foam layer tubes where the foam layer has a comparable density, but different composition, quantitatively and / or qualitatively. .
The cold work hardening behavior as used herein is defined according to Figures 1 and 2. Figure 1 shows a schematic representation of the experimental procedure used to determine cold work hardening. The cold strain hardening behavior of the polymers is analyzed using the Rheotens apparatus 1 (product of Gottfert, Siemensstr. 2, 74711 Buchen, Germany) where a melt strand 2 is elongated by stretching with a defined acceleration. The drag force F is recorded as a function of the drawing speed v. The test procedure is carried out in a standard heated room with a controlled room temperature of T = 23 ° C. The Rheotens apparatus 1 is combined with an extruder / melt pump 3 for continuous feeding of the melt strand 2. The extrusion temperature is 200 ° C; a capillary nozzle with a diameter of 2 mm and a length of 6 mm is used and the acceleration of the bead in the stretched melt state 2 is 120 mm / sec<sup>2</sup>. The schematic diagram in Figure 1 shows, by way of example, the measured increase in drag force F (that is, the "melt strength") versus the increase in drawing speed v (that is, the "capacity stretched ”).
Figure 2 shows the curves recorded in the Rheotens measurements of polymer samples with and without cold work hardening behavior. The maximum points (Fmax; vmax) at bead failure are characteristic of the strength and stretchability of the melt.
Standard propylene polymers 4, 5, 6 with melt indices of 0.3, 2.0 and 3.0 g / 10 min at 230 ° C / 2.16 kg show very low melt strength and low stretching capacity. They do not present
ES 2 219 559 T3 cold strain hardening. Modified propylene polymers 7 (the melt index of the sample in the diagram is 2 to 3 g / 10 min at 230 ° C / 2.16 kg) or LDPE 89 (the melt index of the sample in the diagram is 0.7 g / 10 min at 230 ° C / 2.16 kg) show a completely different behavior of stretchability versus melt strength. As the draw speed v increases, the drag force F increases to a much higher level, compared to standard propylene polymers 4, 5, 6. The shape of this curve is characteristic of cold-strain hardening. The "modified propylene polymers exhibiting cold work hardening behavior" as used herein exhibit improved strength at drag forces F> 15 cN and improved drawability at drag speeds v> 150 mm / s.
The synthetic resin formed by polymerizing propylene as the sole monomer is called polypropylene or propylene polymer. While the terms "polypropylene" or "propylene polymer" have been used from time to time in the art to exclude a copolymer of propylene and a minor amount of another monomer, such as ethylene, such terms are not used herein. mode.
The unmodified propylene polymer as used herein comprises homopolymers of propylene, copolymers of propylene and ethylene and / or α-olefins with 4 to 18 carbon atoms and mixtures of said polymers.
Modified propylene polymers can be obtained by various procedures, for example, by treating the unmodified propylene polymer with radical-forming agents that decompose thermally and / or by treatment with ionizing radiation, where both treatments can be accompanied or followed. , optionally, by a treatment with bi- or multifunctionally unsaturated monomers, for example, butadiene, isoprene, dimethylbutadiene or divinylbenzene. Other processes may be suitable for the production of the modified propylene polymer, provided that the resulting modified propylene polymer meets the characteristics defined in claim 1 with respect to melt index and cold work hardening behavior.
The term "copolymer" as used herein refers particularly to propylene random copolymers, propylene block copolymers, propylene random block copolymers, and elastomeric polypropylenes, but is not limited to such types of copolymers.
In multilayer polyolefin foam tubes, the core tube, which is lined with the polyolefin foam, is a plastic material tube, preferably a propylene polymer tube, or a tube consisting of metal, in particular steel, glass , ceramic material or reinforced duroplastic material, or hollow conductive tubes.
According to an advantageous embodiment, the layer of polyolefinic foam, having a density of 150 to 850 kg / m<sup>3</sup>, comprises mixtures of 5 to 50% by weight of compound A and of 50 to 95% by weight of compound B.
According to another embodiment, the polyolefin foam layer comprises blends containing up to 3% by weight, based on the sum of the propylene polymers, of α-nucleating agents.
Examples of the modified propylene polymers of compound A, prepared by treating unmodified polypropylene with multifunctional, ethylenically unsaturated monomers, in the presence of ionizing radiation or of thermally decomposing free radical-forming agents are, in particular:
• polypropylenes modified by reaction of polypropylenes with bismaleimide compounds in the melt (EP-A-0 574 801 and EP-A-0 574 804), • polypropylenes modified by treatment of polypropylenes with multifunctional monomers, ethylenically unsaturated, under the action ionizing radiation (EP-A-0 678 527), • polypropylenes modified by treatment of polypropylenes with multifunctional, ethylenically unsaturated monomers, in the presence of peroxides in the melt (EP-A-0 688 817 and EP-A-0 450 342).
The modified propylene polymers contained in the polyolefin foam layer are preferably prepared by:
a) mixture of a particulate unmodified propylene polymer, comprising:
a1) propylene homopolymers, especially propylene homopolymers with a MW weight average molecular weight of 500,000 to 1,500,000 g / mol, and / or a2) propylene and ethylene copolymers and / or α- or lefins with 4 to 18 carbon atoms, or mixtures of such copolymers, with 0.05 to 3% by weight, based on the polyolefin composition used, of acyl peroxides, alkyl peroxides, hydroperoxides, peresters and / or peroxycarbonates as generators of free radicals capable of thermal decomposition, if desired diluted with inert solvents, with heating at 30-100 ° C, preferably at 60-90 ° C,
ES 2 219 559 T3
b) sorption of volatile bifunctional monomers by the particulate propylene polymer from the gas phase at a temperature T (° C) of 20 to 120 ° C, preferably 60 to 100 ° C, where the amount of the bifunctional monomers absorbed unsaturates is 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the propylene polymer used, and then
c) heating and melting the particulate polyolefin composition in an atmosphere comprising an inert gas and / or the volatile bifunctional monomers, from the sorption temperature to 200 ° C, after which the free radical generators capable of decomposing decompose thermally and then
d) heating the melt to a temperature of up to 280 ° C in order to separate unreacted monomers and decomposition products,
e) agglomeration of the melt in a manner known per se.
Before step a) and / or e) of the method and / or before or during step c) and / or d) of the method described above, the usual amounts of auxiliary substances can be added, which can be from 0.01 to 2.5% by weight of stabilizers, 0.01 to 1% by weight of processing aids, 0.1 to 1% by weight of antistatics, 0.2 to 3% by weight of pigments and up to 3% by weight of α-nucleating agents, in each case based on the sum of the propylene polymers.
The particulate unmodified propylene polymer can be in the form of powders, granules or sand with grain sizes ranging from 0.001mm to 7mm.
The process for the production of the modified propylene polymer is preferably a continuous method, carried out in continuous reactors, mixers, kneaders and extruders. However, batch production of the modified propylene polymer is also feasible.
The practical sorption times τ of volatile bifunctional monomers range from 10 to 1000 s, with the sorption times τ of 60 to 600 being preferred.
The bifunctionally unsaturated monomers, which are used in the production process of the modified propylene polymers, are preferably C4 to C10 dienes and / or C7 to C10 divinyl compounds. Especially preferred are butadiene, isoprene, dimethylbutadiene or divinylbenzene.
The polymers of compound B are chosen from homopolymers of propylene with a stereospecificity index> 98% and / or copolymers of 91 to 99.9% by weight of propylene and 0.1 to 9% by weight of α-olefins with 2 or 4 to 18 carbon atoms with a stereospecificity index of the propylene homopolymer matrix of> 96%. The stereospecificity index is measured and calculated as described in EP 0 277 514 A2 on page 5 (column 7, line 53 to column 8, line 11).
In general it has been found that, according to the invention, it is convenient to use compounds B with the highest stiffness to obtain polyolefin tubes with an increased compressive strength of the foamed layer. Therefore, it is preferable that the homopolymers of compound B have a stereospecificity index of> 98.9%, with a stereospecificity index of> 98.5% being especially preferred. It is still more preferable that the homopolymers of compound B have a stereospecificity index of> 99.9%. Comparably, when compound B comprises propylene copolymers, either alone or mixed with propylene homopolymers, the following stereospecificity indices of the propylene copolymer homopolymer matrix are preferred: 96% <97% <98% <98 5% <99%, with higher rates being more preferred.
According to an advantageous characteristic of the present invention, the polymers of compound B are obtained by polymerization with a Ziegler-Natta catalytic system comprising solid components containing titanium, an organoaluminum compound as a cocatalyst and an external donor having the general formula
RxR'ySi (RO) 4-xy where R, R 'and R "are identical or different and represent residues of aliphatic or aromatic, branched or cyclic hydrocarbons, and and and x independently of each other are 0 or 1, provided that x + y is 1 or 2. The residues R, R 'and R "can have from 1 to 20 carbon atoms.
Examples of propylene polymers with high stereoregularity, obtained by polymerization with a Ziegler-Natta catalytic system, preferably by gas phase polymerization, are propylene polymers such as those described in EP-A-0.790.262; WO 99 / 24,478 and WO 99 / 16,797.
A preferred external donor in the Ziegler-Natta catalyst system for the production of Compound B polymers is dicyclopentyldimethoxysilane.
For the copolymers of compound B, it is preferable to have a comonomer content of 0.1-10% by weight, preferably 1-8% by weight, with a comonomer content of 2-7% by weight being especially preferred. For the
ES 2 219 559 T3 copolymers of compound B, it is preferable to use ethylene as comonomer.
According to a preferred embodiment of the present invention, the polyolefin foam layer comprises mixtures of 20 to 50% by weight of Compound A with melt indices of 0.3 to 4 g / 10 min at 230 ° C / 2.16 kg and 50 to 80% by weight of compound B with stereospecificity indices of the polypropylene matrix of the order of 97 to 99% and melting indices of the order of 0.1 to 2 g / 10 min at 230 ° C / 2, 16 kg, where compound B consists essentially of propylene block copolymers. In particular, it is preferred in this embodiment that the polymers of compound B have a comonomer content of 3 to 8% by weight.
Auxiliary substances C) optionally contained in single or multilayer polyolefin foam tubes may consist of 0.01 to 2.5% by weight of stabilizers, 0.01 to 1% by weight of processing aids and 0.1 to 1% by weight of antistatics, 0.2 to 3% by weight of pigments and up to 3% by weight of α-nucleating agents and up to 20% by weight of fillers, in each case based on the sum of the propylene polymers.
The stabilizers are preferably mixtures of 0.01 to 0.6% by weight of phenolic antioxidants, 0.01 to 0.6% by weight of 3-arylbenzofuranones, 0.01 to 0.6% by weight of processing stabilizers to phosphite base, 0.01 to 0.6% by weight of high temperature stabilizers based on disulfides and thioethers, and / or 0.01 to 0.8% by weight of hindered amines (HALS).
Suitable phenolic antioxidants are 2-t-butyl-4,6-dimethylphenol, 2,6-di-ti-butyl-4-methylphenol, 2,6-di-t-butyl-4-isoamylphenol, 2,6-di- t-butyl-4-ethylphenol, 2-t-butyl-4,6-diisopropylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2-t-butyl- 4,6-dioctadecylphenol, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-4,4-hexadecyloxyphenol, 2,2'-methylene-bis (6-t-butyl-4-methylphenol ), 4,4'-thio-bis- (6-t-butyl-2-methylphenol), octadecyl-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-butyl-4-hydroxybenzyl) benzene and / or pentaerythritoltetrakis 3- (3,5-di-t-butyl-4- hydroxyphenyl) propionate.
As a benzofuranone derivative, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one is particularly suitable.
As HALS compounds, particularly suitable are bis-2,2,6,6-tetramethyl-4-piperidylsebacate and / or poly1,1,3,3-tetramethylbutyl) -imino) -1,3,5-triazine-2,4 -diyl) (2,2,6,6-tetramethylpiperidyl) -amino) -hexamethylene-4- (2,2,6,6-tetramethyl) piperidyl) -imino).
The α-nucleating agents are preferably talc, sorbitol and sorbitol derivatives, sodium benzoate or the sodium salt of methylene-bis- (2,4-di-t-butylphenol) phosphoric acid. Other nucleating agents that are also suitable are, for example, those described in WO 99/24478.
Processing aids are preferably calcium stearate, magnesium stearate and / or waxes.
An advantageous embodiment of the present invention is a single layer tube in which the single layer is constituted by a layer of polyolefinic foam comprising mixtures of 20 to 80% by weight of compound A with melt indices of 0.3 to 4 g / 10 min at 230 ° C / 2.16 kg and 20 to 80% by weight of compound B with stereospecificity indices of the polypropylene matrix of the order of 98 to 99% and melting indices of the order of 0.1 to 2 g / 10 min at 230 ° C / 2.16 kg, wherein said foam layer has a density of 100 to 850 kg / m<sup>3</sup>.
Preferably, the densities of the polyolefin foam layer of a single layer tube can be 150 to 700 kg / m<sup>3</sup>, densities of 250 to 400 kg / m being especially preferred<sup>3</sup> .
Another advantageous embodiment of the present invention is a multilayer tube wherein the multilayer polyolefin foam tube consists of a steel tube coated with polyolefin and having an inner layer of steel, an intermediate layer of polyolefin foam and a non-foamed polymer outer layer.
According to a preferred embodiment of the present invention, the polyolefin foam layer has a density of 400-850 kg / m<sup>3</sup>, preferably 500-850 kg / m<sup>3</sup>with a density of 550-800 kg / m being especially preferred<sup>3</sup>.
To achieve good interlaminar adhesion between the steel tube and the foamed polyolefin layer, it is convenient to use epoxy resin coated steel tubes and apply a compatibilizing layer between the epoxy resin coated steel tube and the foamed polyolefin layer, where the compatibilizing layer consists of propylene copolymers or propylene polymer graft copolymers, both with carbonic acids and / or carbonic acid anhydrides, ethylenically unsaturated, chemically bound, in particular acrylic acid, methacrylic acid and / or maleic anhydride.
A further embodiment of the present invention is a two-layer polyolefin foam tube, wherein the first layer comprises an unfoamed propylene polymer and the second layer comprises the polyolefin foam layer. In the previous embodiment, tubes are included where the foamed layer is the outer layer and the unfoamed layer is the inner layer, as well as tubes where the unfoamed layer is the outer layer and the foamed layer is the inner layer.
ES 2 219 559 T3
Another advantageous embodiment of the present invention consists of a multilayer polyolefinic foam tube which is constituted by an inner layer of unfoamed polypropylene, an intermediate layer of polyolefinic foam and an outer layer of unfoamed polypropylene.
In the multilayer polyolefin foam tubes of the invention, the unfoamed propylene polymer layer can comprise a wide variety of polymers, eg, rubber modified polypropylenes, filled polypropylenes, polyethylenes, copolymers, etc. The invention is not limited to the aforementioned examples.
Another object of the invention is a process for the production of steel tubes lined with polyolefin foam that have an improved resistance to compression, comprising a steel tube core, an intermediate layer of polyolefin foam and an outer layer of polymer. non-foaming, by extrusion / rotation steel tube coating technology or by crosshead tube coating technology, where the polyolefin foam layer has a density of 400 to 850 kg / m<sup>3</sup> and the polyolefins used in the foam coating are mixtures of:
A) 5 to 80% by weight of a compound A, selected from modified propylene polymers with a melting index of 0.05 to 10 g / 10 min at 230 ° C / 2.16 kg, preferably 0.2 to 10 g / 10 min at 230 ° C / 2.16 kg, whose modified propylene polymers exhibit cold strain hardening behavior, and mixtures of such modified propylene polymers,
B) 20 to 95% by weight of a compound B, selected from propylene homopolymers with a stereospecificity index> 98% and a melting index of 0.05 to 10 g / 10 min at 230 ° C / 2.16 kg , preferably 0.1 to 10 g / 10 min at 230 ° C / 2.16 kg and copolymers of 80 to 99.9% by weight of propylene and 0.1 to 20% by weight of ethylene or alpha-olefins with 4 at 18 carbon atoms with a stereospecificity index of the propylene homopolymer matrix of> 96% and a melt index of 0.1 to 10 g / 10 min at 230 ° C / 2.16 kg, and mixtures of such propylene homopolymers and / or copolymers, and
C) optionally, the usual amounts of stabilizers and / or processing aids and / or antistatics and / or pigments and / or nucleating agents and / or fillers as auxiliary substances, wherein the melt of said mixtures in the coating process with Steel tube foam contains up to 12% by weight, based on the polyolefin blend, of chemical blowing agents that give off gas, or hydrocarbons, halogenated hydrocarbons and / or gases as blowing agents and where the steel tubes are preheated to a temperature preferably between 170 and 230 ° C and the foam liner extruder has a temperature profile that preferably ranges from 175 to 250 ° C .
In the production of the polyolefin foam lined steel pipe by extrusion / rotation steel pipe coating technology, the preheated steel pipe which is optionally coated with an epoxy resin is kept in rotation and successively coated in molten state by independent coating extruders having flat film nozzles layered with the compatibilizing agent, with the foaming propylene polymer blend and the non-foamed polymer top layer.
In the production of polyolefin foam lined steel pipes using crosshead tube lining technology, it is preferable to use a crosshead fed by two extruders, one for the polyolefin foam layer and the second for the layer. non-foamed polymer exterior. The steel tube is pre-treated by optionally coating it with an epoxy resin layer, an adhesive layer and finally a solid layer. Preferably, the steel tube is preheated to a temperature of 170 to 240 ° C before entering the crosshead. The temperature profile at the crosshead is 175 to 250 ° C. The foamed melt is first carried over the pretreated tube, followed by the unfoamed polymer outer layer, after which the coated tube is calibrated on the calibration screen and then cooled. Steel tube diameters on the order of 50 to 500 mm with thicknesses of the polyolefin foam coated layer of up to 200 mm are preferred.
The blowing agents used in the process for the production of single-layer and multi-layer polyolefin foam tubes are chemical agents that emit gas, or hydrocarbons, halogenated hydrocarbons and / or gases. Examples of suitable gas-emitting chemical blowing agents are sodium bicarbonate, azodicarbonamide and / or cyanuric trihydrazide. Suitable hydrocarbons as blowing agents are easily volatile hydrocarbons, such as pentane, isopentane, propane and / or isobutane. Examples of suitable halogenated hydrocarbons are monofluoromethane and / or difluormonochloromethane. Suitable gases as blowing agents are nitrogen, argon and / or carbon dioxide.
A further object of the present invention is a process for the production of tubes of polyolefin foam plastic material with improved resistance to compression by coextrusion or injection molding or blow molding, where at least one of the layers is constituted by a polyolefin foam layer, wherein the polyolefin foam layer has a density of 50 to 850 kg / m<sup>3</sup> and the polyolefins used for the foamed polyolefin layer are mixtures of:
A) 5 to 80% by weight of a compound A, selected from modified propylene polymers with an index of
ES 2 219 559 T3 melt 0.05 to 10 g / 10 min at 230 ° C / 2.16 kg, preferably 0.2 to 10 g / 10 min at 230 ° C / 2.16 kg, whose polymers of modified propylene exhibit cold work hardening behavior, and mixtures of such modified propylene polymers,
B) 20 to 95% by weight of a compound B, selected from propylene homopolymers with a stereospecificity index> 98% and a melting index of 0.05 to 10 g / 10 min at 230 ° C / 2.16 kg , preferably 0.1 to 10 g / 10 min at 230 ° C / 2.16 kg and copolymers of 80 to 99.9% by weight of propylene and 0.1 to 20% by weight of ethylene or alpha-olefins with 4 at 18 carbon atoms with a stereospecificity index of the propylene homopolymer matrix of> 96% and a melt index of 0.1 to 10 g / 10 min at 230 ° C / 2.16 kg, and mixtures of such propylene homopolymers and / or copolymers, and
C) optionally, the usual amounts of stabilizers and / or processing aids and / or antistatics and / or pigments and / or nucleating agents and / or fillers as auxiliary substances, wherein the melt of said mixtures in the foaming process by coextrusion or injection molding or blow molding contains up to 12% by weight, based on the polyolefin blend, of chemical blowing agents that give off gas, or hydrocarbons, halogenated hydrocarbons and / or gases as blowing agents.
In the process for the production of the multilayer polyolefin foam plastic material tubes, the continuous kneaders for the production of the foamed polyolefin layer from the polyolefin mixture containing blowing agents, can consist of single screw extruders. with an L / D ratio of 20 to 40 or in twin screw extruders or cascades of homogenizing extruders (single screw or twin screw) and foaming extruders. Optionally, a melt pump and / or a static mixer can also be used between the extruder and the annular die head. Annular configuration nozzles with diameters between 20 and 800 mm are possible. Convenient temperatures at the nozzle to discharge the melt, which contains the blowing agent, are 160 to 240 ° C. After exiting the annular configuration nozzle, the tubes of multilayer polyolefin foam plastic material are collected in a calibration mandrel, usually accompanied by cooling of the tube by air and / or water, optionally also with internal cooling with water. .
In accordance with one embodiment of the present invention, the polyolefin foam plastic tubes are cut open before being flattened and the resulting multilayer polyolefin foam sheets are optionally rolled.
This method, for example, is described by Djordjevic, D., Rapra Review Report 6 (1992) 2, 51-53.
Preferred applications for single-layer or multi-layer polyolefin foam pipes with improved compressive strength are: coated steel pipes for the transportation of crude oil or gaseous products or heating applications for cities, such as single-layer pipes. single layer for insulating purposes and applications without pressure or low pressure, as well as multilayer plastic pipes for the transport of hot or cold fluids.
In the application as coated steel pipes for the transportation of crude oil from the seabed to tanks, foam densities of the foamed layer between 550 and 850 kg / m are preferred.<sup>3</sup>. In order to be able to pump crude oil from reservoirs located in cold maritime regions, the fluid has to be kept warm enough. By using the insulating layer based on foamed polypropylene of the invention, it is possible to avoid strong heat losses to the surrounding water and also to eliminate additional and expensive oil heating units along the pipeline. However, at water depths of 200 to 300 m (up to 600 m with the now existing materials), the pressures are important and a high mechanical stability of the foamed insulating layer is required. The foam layers of the invention in fact exhibit an outstanding balance between thermal insulation efficiency and compressive strength.
Steel pipes lined with foam layers according to the invention (for example, according to example 3) can withstand pressures corresponding to water depths greater than 2,000 m with foam densities of the foamed layer between 550 and 850 kg / m<sup>3</sup>. With varying compositions, ie with different A / B ratios, even higher compressive strengths (corresponding to water depths ranging up to 3,000 m) can be achieved. Therefore, it is possible to use the tubes according to the invention in even greater water depths than is possible today with foam densities of the foamed layer between 550 and 850 kg / m<sup>3</sup>. These tubes have a thermal insulation capacity comparable to that of currently used tubes. Tubes with lower foamed layer densities can be used at current depths (up to 600 m). These tubes have the advantage of a better thermal insulation capacity.
In their application as tubes of multilayer polyolefin foam plastic material for the transport of hot and cold fluids, the tubes of the invention can preferably be used to transport and conduct hot and / or cold water in indoor applications.
The special advantage of the single-layer or multi-layer tubes of the invention resides in that, based on
ES 2 219 559 T3 the propylene polymer blends of the invention for the foam layers, single-layer or multi-layer tubes can be produced having, in the polyolefin foam layer, a uniform distribution of the cells of the foam and a high strength of the foam layer and therefore exhibit an outstanding balance between thermal insulation efficiency and compressive strength.
Examples
The following tests were carried out:
Tensile modulus according to ISO 527 (crosshead speed 1mm / min)
Impact resistance with Charpy notch according to ISO 179/1 eA
Compressive strength according to ASTM D 695-96 (compression 5%)
Example 1
1.1 Synthesis of the modified propylene polymer A)
A powdered polypropylene homopolymer, with a melt index of 0.25 g / 10 min at 230 ° C / 2.16 kg and an average particle size of 0.45 mm, is continuously metered into a continuous paddle mixer under an inert atmosphere (nitrogen). Furthermore, 0.65% by weight of tert-butylperoxyisopropyl carbonate and 0.15% by weight of butadiene are continuously metered into the mixer, in each case based on the propylene homopolymer. While homogeneously mixed at 60 ° C, the propylene homopolymer, loaded with the thermally decomposing free radical forming agent and auxiliary material, is absorptively introduced for a residence time of 10 min. After transfer to a twin screw extruder, the filled polypropylene powder is melted at a mass temperature of 230 ° C and, after passing through a degassing zone, is added to the melt and mixed smoothly. homogeneous 0.1% by weight of tris- (2,4-di-tert-butylphenyl) phosphite, 0.1% by weight of calcium stearate and 0.05% by weight of hydrotalcite. The melt is then pelleted.
The resulting modified propylene polymer A) has a melt index of 2.3 g / 10 min at 230 ° C / 2.16 kg and shows cold strain hardening behavior as characterized by Rheotens values of Fmax = 33 cN and Vmax = 210mm / s, measured at the chord failure point.
.2 Preparation of the polyolefin mixture
A mixture of 30% by weight of modified propylene polymer A) having a melt index of 2.3 g / 10 min at 230 ° C / 2.16 kg and Rheotens values of F<sub>max</sub> = 33 cN and V<sub>max</sub> = 210 mm / s, measured at the point of failure of the cord, and 70% by weight of a propylene block copolymer B) having an ethylene content of 5% by weight, a stereospecificity index of 98.7% and a melting index of 0.30 g / 10 min at 230 ° C / 2.16 kg and whose mixture contains 0.25% by weight of pentaerythrityl-tetrakis (3- (3 ', 5'-di-tert) butyl-4-hydroxyphenyl) -propionate), 0.15% by weight of tris (2,4-di-tert-butylphenyl) phosphite, 0.2% by weight of distearyl thiodipropionate and 0.7% by weight of calcium stearate, melted and homogenized in a Werner & Pfleiderer ZSK 92 twin screw extruder with a temperature profile of 175 to 250 ° C, discharges and granulates. The resulting propylene compound has a melt index of 0.38 g / 10 min, a tensile modulus of 1,740 MPa and a Charpa notched impact resistance at -20 ° C of 2.5 kJ / m<sup>2</sup>.
1.3 Preparation of steel tube lined with polyolefin foam
The pilot scale steel pipe coating line consists of a preheating unit, two extruders, two nozzle heads and the cooling unit. The line is designed so that the adhesive layer is added first and then the foamed layer before starting the cooling.
A steel tube (diameter 150 mm) coated with a 25 μιη epoxy resin layer and a 30 μιη compatibilizing layer of maleic anhydride grafted propylene polymer (0.20% by weight of maleic anhydride), which has been preheated at a temperature of 190 ° C, it is driven forward at a speed of 1.2 m / min. The stabilized polypropylene blend of the modified polypropylene A) and the propylene block copolymer B) as described in 1.2, is dry mixed with 2.2% by weight, based on the propylene compound, with a mixture of agent Bicarbonate and citric acid based expansion agent. The resulting mixture is supplied by means of a metering system to the feed hopper of the extruder with a temperature profile of 175 to 250 ° C. Initially, the mixture is melted and homogenized, and then the blowing gas emitted from the extruder is intensively mixed and homogeneously distributed.
The melt is then transferred through the flat nozzle head and incorporated onto the steel tube, after which the coated tube is cooled with water. From the steel tube lined with polyolefin foam, test specimens 254 mm in length are cut. The polyolefin foam layer has a thickness of 50 mm and a density of 720 kg / m<sup>3</sup>. The non-foamed cover layer is 8 mm thick.
ES 2 219 559 T3
Example 2
2.1 Synthesis of the modified propylene polymer A)
A powdered random propylene copolymer containing 6% by weight of ethylene with a melt index of 0.23 g / 10 min at 230 ° C / 2.6 kg and an average particle size of 0.45 mm, it is continuously metered into a continuous paddle mixer under an inert nitrogen atmosphere. Furthermore, 0.23% by weight of tert-butyl peroxybenzoate and 0.33% by weight of divinylbenzene are continuously metered into the mixer, in each case based on the propylene polymer. While homogeneously mixed at 70 ° C, the powdered propylene homopolymer is absorptively charged with these substances for a residence time of 20 min. After transfer to a twin screw extruder, the filled polypropylene powder is melted at a mass temperature of 230 ° C and, after passing through a degassing zone, 0 is added to the melt, with homogenization. , 1% by weight of tris- (2,4-di-tert-butylphenyl) phosphite and 0.1% by weight of calcium stearate. Then the melt is pelleted. The resulting modified propylene polymer A) has a melt index of 0.52 g / 10 min at 230 ° C / 2.16 kg and shows cold strain hardening behavior characterized by Rheotens values of Fmax = 38.2 cN and Vmax = 192 mm / s, measured at the point of failure of the bead.
2.2. Preparation of the polyolefin mixture
A mixture of 40% by weight of modified propylene polymer A) having a melt index of 0.52 g / 10 min at 230 ° C / 2.16 kg and Rheotens values of F<sub>max</sub> = 38.2 cN and V<sub>max</sub> = 192 mm / s, measured at the point of failure of the cord, and 60% by weight of a propylene block copolymer B) having an ethylene content of 5% by weight, a stereospecificity index of 98.7% and a melting index of 0.30 g / 10 min at 230 ° C / 2.16 kg and whose mixture contains 0.25% by weight of pentaerythrityl-tetrakis (3- (3 ', 5'-di-tert) butyl-4-hydroxyphenyl) -propionate), 0.15% by weight of tris (2,4-di-tert-butylphenyl) phosphite, 0.2% by weight of distearyl thiodipropionate and 0.7% by weight of calcium stearate, is melted and homogenized in a Werner & Pfleiderer ZSK 92 twin screw extruder with a temperature profile of 175 to 250 ° C, discharged and granulated. The resulting propylene compound has a melt index of 0.35 g / 10 min.
2.3 Preparation of multilayer polyolefin foam tube
Three-layer polyolefin foam tubes having an outer diameter of 200mm were extruded by a conventional tube extruder having a screw diameter of 60mm and by two conventional side extruders having a screw diameter of 50mm, all connected to a multilayer tool to extrude three layers of variable thickness of the materials and with also variable composition of the layers. The linear speed was 0.9 m / min, the temperature of the mass of the polyolefin mixture containing foaming agent was 190 ° C, and the temperature of the non-foamed propylene polymer was 210 ° C.
Both 50mm extruders producing the unfoamed inner and outer layers of the multilayer polyolefin foam tube were fed with a polypropylene homopolymer with a melt index of 0.3 g / 10 min at 230 ° C / 2.16 kg. The 60 mm extruder (L / D 35, temperature profile 175-230 ° C) was fed with the polyolefin mixture described in 2.2 of a modified propylene copolymer and a propylene block copolymer, then dry mixing with 3% by weight, based on the sum of the polyolefins, of a blowing agent mixture, based on bicarbonate and citric acid. Initially, the mixture is melted and homogenized, and then the emitted blowing gas is mixed intensively in the extruder and homogeneously distributed throughout the melt. Next, the melt is transferred through the multilayer annular nozzle tool and the multilayer tube is cooled by a water cooling device.
The resulting three-layer polyolefin foam tube has an outer diameter of 200 mm, the thickness of the outer layer being 1 mm, the thickness of the intermediate layer of foamed polyolefin being 6 mm, where the foam layer, which has a tiny, closed-cell foam structure, has a density of 365 kg / m<sup>3</sup>, the interior layer being 2m thick without foam.
Example 3
Polyolefin foam layers comprising blends of 30% by weight of Compound A, which is a propylene homopolymer with a melt index of 2.3 g / 10 min at 230 ° C / 2.16 kg and a cold work hardening behavior expressed by Rheotens values of Fmax = 33 cN and Vmax = 210 mm / s and 70% by weight of compound B), which is a propylene block copolymer containing 5.2% by weight of ethylene, and which has a melt index of 0.25 g / 10 min at 230 ° C / 2.16 kg and with a stereospecificity of the matrix 98.7% propylene homopolymer. Compound B and a reference polymer were also foamed to form polyolefin foam layer samples (ethylene content = 8% by weight, melt index = 0.27 g / 10 min at 230 ° C / 2, 16 kg, stereospecificity = 97.4%). The thermal conductivity was determined according to ASTM C-518 and the compressive strength, with a compression of 5%, of the samples was determined according to ASTM D 695-96. The following results were obtained:
ES 2 219 559 T3
<td>Product</td><td>Density [kg / m<sup>3</sup>]</td><td>Tensile Modulus | MPa]</td><td>K value | W / mK]</td><td>Compressive strength IMPal</td>
<td>reference</td><td> 737</td><td> 900</td><td> 0.18</td><td> 12,6</td>
<td>reference</td><td> 820</td><td> 950</td><td> 0.20</td><td> 17</td>
<td>100% B</td><td> 734</td><td> 1000</td><td> -</td><td> 14</td>
<td>100% B</td><td> 643</td><td> 830</td><td> 0,16</td><td> 11</td>
<td>30% A + 70% B</td><td> 727</td><td> 1200</td><td> 0,177</td><td> 22</td>
<td>30% A + 70% B</td><td> 759</td><td> 1270</td><td> 0,184</td><td> 23</td>
<td>30% A + 70% B</td><td> 653</td><td> 950</td><td> 0,161</td><td> 17</td>
<td>30% A + 70% B</td><td> 699</td><td> 1040</td><td> 0,168</td><td> 19</td>
<td>30% A + 70% B</td><td> 616</td><td> 730</td><td> 0,149</td><td> 15</td>
Contents6
1 sheet
Sheet 1
19 members in 9 offices
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 00115636 | European Patent Office (EPO) | A | |
| 20000115636 | European Patent Office (EPO) | – |
Members19
| Document | Office | Kind | |
|---|---|---|---|
| EP1174261A1 | European Patent Office (EPO) | A1 | |
| WO0207969A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU8581901A | Australia | A | |
| NO20030218D0 | Norway | D0 | |
| NO20030218L | Norway | L | |
| EP1301343A1 | European Patent Office (EPO) | A1 | |
| BR0112594A | Brazil | A | |
| US2003157286A1 | United States of America | A1 | |
| EP1301343B1 | European Patent Office (EPO) | B1 | |
| AT264751T | Austria | T | |
| ATE264751T1 | Austria | T1 | |
| DE60102929D1 | Germany | D1 | |
| ES2219559T3This record | Spain | T3 | |
| DE60102929T2 | Germany | T2 | |
| US6986922B2 | United States of America | B2 | |
| US2006233989A1 | United States of America | A1 | |
| US7462307B2 | United States of America | B2 | |
| BR0112594B1 | Brazil | B1 | |
| NO333461B1 | Norway | B1 |
Numbers
- Publication
- 2219559
- Application
- 1965099
Titles2
- Spanish
- TUBOS DE ESPUMA POLIOLEFINICA DE UNA SOLA CAPA Y DE MULTIPLES CAPAS.
- English
- POLYOLEFINIC FOAM PIPES OF A SINGLE COAT AND MULTIPLE LAYERS.
Classification
- CPC, 39
- C08L23/142
- B32B5/18
- B32B15/08
- B32B27/32
- C08L23/12
- C08L23/14
- C08L51/06
- C08L53/00
- F16L59/02
- F16L59/143
- C08J9/0023
- C08J2201/03
- C08J2323/12
- C08J9/0061
- C08J9/08
- C08J9/122
- C08J9/141
- C08J9/143
- C08J2201/026
- C08J2323/14
- C08J2323/16
- C08J2353/00
- C08J2423/12
- C08J2423/14
- C08J2423/16
- C08J2453/00
- B29K2995/0063
- B29K2023/06
- B29K2023/12
- B29C44/324
- B29C44/5627
- Y10T428/139
- Y10T428/1393
- Y10T428/1376
- Y10T428/1397
- Y10T428/249988
- Y10T428/249993
- Y10T428/249989
- Y10T428/249958
- IPC, 10
- B32B5 18
- B32B15 08
- B32B27 32
- C08L23 12
- C08L23 14
- C08L51 06
- C08L53 00
- F16L9 12
- F16L59 02
- F16L59 14