ES2665963T3 - Filamento o fibra de polímero - Google Patents

Filamento o fibra de polímero Download PDF

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Publication number
ES2665963T3
ES2665963T3 ES11715557.2T ES11715557T ES2665963T3 ES 2665963 T3 ES2665963 T3 ES 2665963T3 ES 11715557 T ES11715557 T ES 11715557T ES 2665963 T3 ES2665963 T3 ES 2665963T3
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Prior art keywords
filament
iso
accordance
value
stretching
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Gianni Perdomi
Fabiana Fantinel
Roberto Vanzini
Shahram Mihan
Roberto De Palo
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Basell Polyolefine GmbH
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Basell Polyolefine GmbH
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
    • E01C13/08—Surfaces simulating grass ; Grass-grown sports grounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Architecture (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un filamento o fibra de polímero que comprende un material de polietileno (I) que tiene las siguientes características: a) una densidad de 0,925 g/cm3 a 0,945 g/cm3, medida de acuerdo con ISO 1183; b) un valor de MI21 de 25 g/10 min. o mayor, preferiblemente de 30 g/10 min. o mayor, más preferiblemente de 35 g/10 min. o mayor, donde MI21 es el Índice de fusión a 190°C con una carga de 21,6 kg, determinada de acuerdo con ISO 1133; c) un valor de MFR de 25 a 60, donde MFR significa velocidad de flujo en estado fundido y es la relación entre MI2 y MI2, donde MI2 es el índice de fusión a 190°C con una carga de 2,16 kg, determinada de acuerdo con ISO 1133; d) un valor Mw/Mn de 6 o mayor, donde Mw es la masa molar promedio en peso, Mn es la masa molar promedio en número, ambas medidas por GPC (Cromatografía de Permeación por Gel); siendo dicha fibra estirada mediante estiraje con una relación de estiraje de 1,5 a 10.

Description

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5 
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El filamento de poliolefina de la invención puede prepararse por medio de procesos y aparatos bien conocidos en la técnica relevante.
En términos generales, el proceso para preparar filamentos de poliolefina de acuerdo con la invención comprende los siguientes pasos:
(a)
fusionar el material de polietileno (I) y los otros componentes de poliolefina, cuando están presentes;
(b)
tejer los filamentos o extrudir una película o cinta precursora;
(c)
opcionalmente estirar los filamentos o la película o cinta precursora y/o cortar la película o cinta precursora y opcionalmente estirar los filamentos obtenidos de este modo, cuando no se lleva a cabo estiraje previo;
(d)
opcionalmente terminar los filamentos obtenidos del paso (b).
El paso de fusión (a) y el paso de hilado o extrusión (b) se llevan a cabo en general de manera continua en secuencia al usar extrusores de doble tornillo o un solo tornillo, equipados con una cabeza de hilado o extrusión adecuada. Por lo tanto el paso de fusión-mezclado descrito anteriormente puede llevarse a cabo en el mismo aparato de hilado o extrusión usado en el paso (b).
Las cabezas de hilado comprenden una pluralidad de agujeros con la misma forma que la sección transversal del filamento (monofilamento o cinta).
Las cabezas de extrusión de película en general son troqueles planos o anulares comúnmente usados para la preparación de películas.
Cuando una película o cinta precursora se obtiene en el paso (b), se procesa entonces en el paso (c) al cortarla en cintas que tienen el tamaño deseado. Cuando el tratamiento de estiraje se lleva a cabo en la película o cinta precursora, consecuentemente ya no se requiere en el filamento final.
Ejemplos de tratamientos de acabado pueden ser fibrilación y prensado.
La fibrilación en general se lleva a cabo en cintas.
Típicamente el paso de fusión (a) y el paso de hilado o extrusión (b) se llevan a cabo a las mismas temperaturas que las definidas previamente para el paso de fusión-mezclado, principalmente de 180 a 310°C, preferiblemente de 190 a 280°C, más preferiblemente de 200 a 250°C.
Las condiciones de hilado típicas son:
 temperatura en la cabeza del extrusor de 200 a 300°C;  velocidad tensora para una red primaria (sin estirar) de 1 a 50 m/min.
Las condiciones de extrusión de película típicas son:
 temperatura en la cabeza del extrusor de 200 a 300°C;  valor de salida de 20 a 1000 kg/hora (en plantas industriales).
El filamento o la película precursora obtenidos en el paso (b) se enfrían en general al usar por ejemplo uno o más rodillos enfriadores o mediante inmersión en agua a una temperatura de 5 a 25°C.
Para llevar a cabo el tratamiento de estiraje, el filamento (monofilamento o cinta) o la cinta precursora se calientan previamente a una temperatura de 40 a 120-140°C. El calentamiento puede alcanzarse usando por ejemplo un horno de aire caliente, un baño de agua hirviendo, rodillos calientes o mediante irradiación u otros medios conocidos.
El estiraje puede alcanzarse al pasar el filamento o la cinta precursora a través de una serie de rodillos que tienen diferentes velocidades de rotación. Los rangos preferidos de relaciones de estiraje alcanzados así son aquellos previamente especificados.
La fibrilación puede alcanzarse al alimentar la cinta entre los rodillos que tienen medios para cortar longitudinalmente y/o diagonalmente.
Las fibras con denier más bajo que los filamentos, a saber, con un título por debajo de los 20 dTex, típicamente de 1 a 15 dTex, se preparan al extruir la fusión de polímero a través de las cabezas de hilado ya descritas, en donde los agujeros tienen un diámetro más pequeño con respecto al diámetro usado para filamentos. Las fibras que emergen de la cabeza de hilado se someten posteriormente a aplacado y se orientan al estirarse de manera similar a la descrita anteriormente con referencia a la orientación de los filamentos.
9
imagen8
Composición de copolímeros
La distribución de díadas se calcula de espectros 13C NMR usando las siguientes relaciones: PP= 100 I1/Σ
5  PB = 100 I2/Σ BB = 100 (I3 -I19)/Σ PE = 100 (I5 + I6)/Σ BE =100 (I9 + I10)/Σ EE = 100 (0,5(I15 + I6 + I10) + 0,25 (I14))/Σ
10  Donde Σ = I1 + I2 + I3 - I19 + I5 + I6 +I9 + I6 + I10+ 0,5(I15 + I6 + I10) + 0,25 (I14) El contenido molar se obtiene de díadas usando las siguientes relaciones: P (m%)= PP + 0,5 (PE+PB) B (m%)= BB + 0,5 (BE+PB) E (m%)= EE + 0,5 (PE+BE)
15  I1, I2, I3, I5, I6, I9, I6, I10, I14, I15, I19 son integrales de los picos en el espectro de 13C NMR (pico de la secuencia EEE a 22,9 ppm como referencia). Las asignaciones de estos picos se realizan de acuerdo con J.C. Randal, Macromol. Chem Phys., C29, 201 (1989),
M. Kakugo, Y. Naito, K. Mizunuma y T. Miyatake, Macromolecules, 15, 1150, (1982) y H.N. Cheng, Journal of
Polymer Science, Polymer Physics Edition, 21, 57 (1983). Se recogen en la Tabla A (nomenclatura de acuerdo con 20 C.J. Carman, R.A. Harrington y C.E. Wilkes, Macromolecules, 10, 536 (1977)).
Tabla A.
I
Desplazamiento químico (ppm) Carbono Secuencia
1
47,34 - 45,60 Sαα PP
2
44,07 - 42,15 Sαα PB
3
40,10 - 39,12 Sαα BB
4
39,59 Tδδ EBE
5
38,66 - 37,66 Sαγ PEP
6
37,66 - 37,32 Sαδ PEE
7
37,24 Tβδ BBE
8
35,22 - 34,85 Tββ XBX
9
34,85 - 34,49 Sαγ BBE
10
34,49 - 34,00 Sαδ BEE
11
33,17 Tδδ EPE
12
30,91 - 30,82 Tβδ XPE
13
30,78 - 30,62 Sγγ XEEX
14
30,52 - 30,14 Sγδ XEEE
15
29,87 Sδδ EEE
16
28,76 Tββ XPX
17
28,28 - 27,54 2B2 XBX
18
27,54 - 26,81 Sβδ + 2B2 BE, PE, BBE
19
26,67 2B2 EBE
20
24,64 - 24,14 Sββ XEX
21
21,80 - 19,50 ch3 P
22
11,01 - 10,79 ch3 B
Determinación del contenido de pentadas isotácticas
25 
Se disolvieron 50 mg de cada muestra en 0,5 mL de C2D2Cl4. Los espectros de 13C NMR fueron adquiridos en un Bruker DPX-400 (100,61 Mhz, 90° de pulso, 12s de retraso entre los pulsos). Se almacenaron aproximadamente 3000 transitorios para cada espectro; se usó un pico de pentada mmmm (27,73 ppm) como referencia.
30  El análisis de la microestructura se llevó a cabo como se describe en la literatura (Macromolecules 1991, 24, 23342340, por Asakura T. et Al. . y Polymer, 1994, 35, 339, por Chujo R. et al.).
11
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Claims (1)

  1. imagen1
ES11715557.2T 2010-04-30 2011-04-21 Filamento o fibra de polímero Active ES2665963T3 (es)

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EP10161540 2010-04-30
EP10161540 2010-04-30
US40103810P 2010-08-06 2010-08-06
US401038P 2010-08-06
PCT/EP2011/056449 WO2011134897A2 (en) 2010-04-30 2011-04-21 Polymer filament or fiber

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EP3054038B1 (en) * 2015-02-06 2025-02-12 Dow Global Technologies LLC Method of manufacturing an artificial turf filament
EP3741886A1 (en) 2016-10-31 2020-11-25 Polytex Sportbeläge Produktions-GmbH Artificial turf fiber from renewable biomass
TW201903229A (zh) * 2017-06-06 2019-01-16 比利時商道達爾研究及技術弗呂公司 聚乙烯布、以及由其製成的襯裡和人造草皮
JP7114361B2 (ja) 2018-06-19 2022-08-08 サンアロマー株式会社 ポリプロピレン組成物および成形品
JP7249126B2 (ja) 2018-10-18 2023-03-30 サンアロマー株式会社 ポリプロピレン組成物および成形品
RU2709407C1 (ru) * 2019-03-29 2019-12-17 Российская Федерация в лице Федерального государственного бюджетного образовательного учреждения высшего образования "Тверской государственный университет" ИК-спектроскопический способ контроля качества прекурсоров для ориентационного вытягивания пленочных нитей из сверхвысокомолекулярного полиэтилена
PT4069774T (pt) 2019-12-03 2024-02-05 Basell Polyolefine Gmbh Composição de polietileno para filamentos ou fibras
CN114641526A (zh) * 2019-12-03 2022-06-17 巴塞尔聚烯烃股份有限公司 用于长丝或纤维的聚乙烯组合物
CN117794996A (zh) * 2021-08-18 2024-03-29 巴塞尔聚烯烃股份有限公司 用于长丝或纤维的聚烯烃组合物

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US9605360B2 (en) 2017-03-28
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EP2563957A2 (en) 2013-03-06
US20130064995A1 (en) 2013-03-14

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