WO2011144486A1 - Cuve en polypropylène pour machine à laver - Google Patents

Cuve en polypropylène pour machine à laver Download PDF

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Publication number
WO2011144486A1
WO2011144486A1 PCT/EP2011/057471 EP2011057471W WO2011144486A1 WO 2011144486 A1 WO2011144486 A1 WO 2011144486A1 EP 2011057471 W EP2011057471 W EP 2011057471W WO 2011144486 A1 WO2011144486 A1 WO 2011144486A1
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WO
WIPO (PCT)
Prior art keywords
weight
tub
component
polypropylene resin
propylene
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PCT/EP2011/057471
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English (en)
Inventor
Marco Ciarafoni
Manikandan Rathinakumar
Paola Massari
Jackie Tong
Original Assignee
Basell Poliolefine Italia Srl
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Publication date
Application filed by Basell Poliolefine Italia Srl filed Critical Basell Poliolefine Italia Srl
Priority to CN201180024790.1A priority Critical patent/CN102884123B/zh
Publication of WO2011144486A1 publication Critical patent/WO2011144486A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene

Definitions

  • the present invention relates to the use of a particular polypropylene resin for obtaining tubs for washing machines, more specifically dishwashers and clothes washing machines.
  • Tubs for washing machines can be divided in two categories, tubs rotating through the horizontal axis and fixed tubs having an opening in the bottom for the agitator or pulsator rotating through the vertical axis.
  • the two type of tubs have different characteristics since they are stressed in a different way.
  • the present invention is limited to washing machines having a fixed tub wherein the agitator rotates on a vertical axis.
  • US 6,716,383 relates to a washing tub formed by a reinforcing body made from a non-metallic material, such as plastic or fiberglass, and a thin interior liner portion constituted by a metallic material.
  • the reinforcing body is formed from plastic, such as polypropylene. This document is silent about the type of polypropylene resin that can be used.
  • US 2006/0086379 relates to a method for improving stain resistance of a plastic washing machine component arranged within a wash chamber of a washing machine. Also this document relates generally to polypropylene without specifying its features.
  • An object of the present invention is therefore a process for producing a fixed tub of a washing machine comprising the step of injection molding a polypropylene resin in the form of the tub; wherein the polypropylene resin comprises (percent by weight):
  • the polypropylene resin to be used in the process of the present invention has an intrinsic viscosity of the fraction soluble in xylene at 25 °C comprised between 2.0 and 5.0 dl/g; preferably between 2.5 and 4.0 dl/g more preferably between 2.9 and 3.5 dl/g and a MFR L (Melt Flow Rate according to ISO 1133, condition L, i.e. 230°C and 2.16 kg load) from 30 to 100 g/10 min preferably from 40 to 90 g/10 min more preferably from 50 to 80 g/10 min; even more preferably from 55 to 70 g/10 min.
  • MFR L Melt Flow Rate according to ISO 1133, condition L, i.e. 230°C and 2.16 kg load
  • copolymer includes polymers containing only two kinds of comonomers.
  • component A) is a propylene homopolymer
  • polypropylene resin to be used in the process of the present invention are:
  • the Flexural Modulus preferably comprised between 1000 MPa and 2000 MPa, more preferably comprised between 1100 and 1800 MPa; even more preferably comprised between 1200 and 1700 MPa
  • the propylene polymer compositions of the present invention can be prepared by sequential polymerization in at least two stages, with each subsequent polymerization stage being conducted in the presence of the polymeric material formed in the immediately preceding polymerization reaction, wherein the polymer (A) is normally prepared in at least one first polymerization stage and the copolymer (B) is normally prepared in at least one second polymerization stage.
  • each polymerization stage is carried out in presence of a highly stereospecific heterogeneous Ziegler-Natta catalyst.
  • the Ziegler-Natta catalysts suitable for producing the propylene polymer compositions of the invention comprise a solid catalyst component comprising at least one titanium compound having at least one titanium-halogen bond and at least an electron-donor compound (internal donor), both supported on magnesium chloride.
  • the Ziegler-Natta catalysts systems further comprise an organo-aluminum compound as essential co- catalyst and optionally an external electron-donor compound.
  • Suitable catalysts systems are described in the European patents EP45977, EP361494, EP728769, EP 1272533 and in the international patent application W000163261.
  • the solid catalyst component comprises Mg, Ti, halogen and an electron donor.
  • the electron donor can be selected from succinates of formula (I):
  • radicals R and R are a C 1 -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms belonging to groups 15-17 of the periodic table;
  • the radicals R 3 to R 6 equal to or different from each other, are hydrogen or a C 1 -C 2 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms, and the radicals R 3 to R 6 which are joined to the same carbon atom can be linked together to form a cycle.
  • R 1 and R 2 are preferably Ci-Cs alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups.
  • R and R are selected from primary alkyls and in particular branched primary alkyls.
  • suitable R 1 and R 2 groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.
  • Particularly preferred are ethyl, isobutyl, and neopentyl.
  • R 3 to R 5 are hydrogen and R 6 is a branched alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl radical having from 3 to 10 carbon atoms.
  • R 6 is a branched alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl radical having from 3 to 10 carbon atoms.
  • Another preferred group of compounds within those of formula (I) is that in which at least two radicals from R 3 to R 6 are different from hydrogen and are selected from C 1 -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms belonging to groups.
  • the electron donor can be of the type described in EP 09163192.9.
  • the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR) n _ y X y where n is the valence of titanium and y is a number between 1 and n, preferably TiC4, with a magnesium chloride deriving from an adduct of formula MgCl 2 pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
  • the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130 "C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in US 4,399,054 and US 4,469,648.
  • the so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130 °C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCU (generally 0 °C); the mixture is heated up to 80-130 °C and kept at this temperature for 0.5-2 hours.
  • the treatment with Tic4 can be carried out one or more times.
  • the internal donor can be added during the treatment with T1CI 4 and the treatment with the electron donor compound can be repeated one or more times.
  • the succinate of formula (I) is used in molar ratio with respect to the MgC12 of from 0.01 to 1 preferably from 0.05 to 0.5.
  • the preparation of catalyst components in spherical form is described for example in European patent application EP-A-395083 and in the International patent application W098144001.
  • the solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) generally between 20 and 500 m21g and preferably between 50 and 400 m21g, and a total porosity (by B.E.T. method) higher than 0.2 cm31 g preferably between 0.2 and 0.6 cm31g.
  • the porosity (Hg method) due to pores with radius up to 10.000A generally ranges from 0.3 to 1.5 cm31g, preferably from 0.45 to 1 cm31g.
  • the organo -aluminum compound is preferably an alkyl-Al selected from the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri- n-hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of trialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as
  • Preferred external electron-donor compounds include silicon compounds, ethers, esters such as ethyl 4-ethoxybenzoate, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethyl piperidine, ketones and the 1,3-diethers.
  • Another class of preferred external donor compounds is that of silicon compounds of formula R a 5 Rt, 6 Si(OR 7 ) c where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R 5 , R 6 , and R 7 , are alkyl, cycloalkyl or aryl radicals with 1 -18 carbon atoms optionally containing heteroatoms.
  • methylcyclohexyldimethoxysilane diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane and 1,1 ,1 ,trifiuoropropyl-2-ethylpiperidinyl-dimethoxysilane and 1,1,1 ,trifluoropropyl- metildimethoxysilane.
  • the external electron donor compound is used in such an amount to give a molar ratio between the organo-aluminum compound and said electron donor compound of from 0.1 to 500.
  • the polymerization process can be carried out in gas phase and/or in liquid phase, in continuous or batch reactors, such as fiuidized bed or slurry reactors.
  • continuous or batch reactors such as fiuidized bed or slurry reactors.
  • all the sequential polymerization stages can be carried out in gas phase.
  • the reaction time, temperature and pressure of the polymerization steps are not critical, however the temperature for the preparation of fraction (A) and (B), that can be the same or different, is usually from 50°C to 120°C.
  • the polymerization pressure preferably ranges from 0.5 to 12 MPa if the polymerization is carried out in gas-phase.
  • the catalytic system can be pre-contacted (pre- polymerized) with small amounts of olefins.
  • the molecular weight of the propylene polymer composition is regulated by using known regulators, such as hydrogen.
  • the propylene/ethylene copolymer (B) is produced in a conventional fluidized-bed gas-phase reactor in the presence of the polymeric material and the catalyst system coming from the preceding polymerization step.
  • the propylene polymer compositions of the present invention can also be obtained by separately preparing the said copolymers (A) and (B), operating with the same catalysts and substantially under the same polymerization conditions as previously illustrated and subsequently mechanically blending said copolymers in the molten state using conventional mixing apparatuses, like twin-screw extruders.
  • the polypropylene resin to be used in the process of the present invention may further comprise additives commonly employed in the polyolefin field, such as antioxidants, light stabilizers, nucleating agents, antiacids, colorants and fillers.
  • additives commonly employed in the polyolefin field such as antioxidants, light stabilizers, nucleating agents, antiacids, colorants and fillers.
  • the polypropylene resin can be molded and injected according to the process of the present invention with processes commonly know in the art.
  • a further object of the present invention is the use of the polypropylene resin comprising component A) and component B) as described above for the production of fixed tubs for washing machines.
  • a further object of the present invention is a fixed tub for washing machines characterized by being made of polypropylene resin comprising component A) and component B) as described above.
  • the fixed tub has a cylindrical or parallelepipedal shape and at least one opening in the bottom part.
  • the fixed tub is divided in two chambers one used as washing chamber and presenting the opening in the bottom part, the second being used as drying chamber.
  • a still further object of the present invention is a washing machine comprising a fixed tub as described above.
  • FIG. 1 shows a partially broken elevational sectional view of a clothes washing machine wherein the tub is made of polypropylene resin in accordance with the present invention
  • the washing machine comprises a washing tub 1 arranged at a side inside the housing 2 and a dryer tub 3 arranged at the other side, which washing tub 1 is provided with an opening 6 for the roller type agitator on the bottom and a driving mechanism 5 equipped under the bottom thereof.
  • Figure 2 shows the partially broken elevational sectional view described in figure 1 wherein the tub made in polypropylene resin according to the present invention is divided in two chambers, a washing chamber 11 and a drying chamber 13, by a dividing plate 17 that can be a fixed plate so that the whole tub divided in two chambers is directly obtained by injection moulding as a whole shape, or a removable plate.
  • FIG. 3 describes a dishwasher tub 21 obtained with the process according to the present invention.
  • dishwasher tub 21 includes an outer body portion 22 and an inner liner portion 23. More specifically, dishwasher tub 21 includes opposing sides 24 and 25, a top 26 and a bottom 27. Furthermore, dishwasher tub 22 is provided with a substantially central opening 28 formed in bottom 27.
  • FIG. 4 describes the load test carried out to evaluate the stiffness of the tub of the present invention.
  • the tub 31 comprises a washing chamber 32 having an opening on the bottom part 36 and a drying chamber 33, the washing chamber and the drying chamber are created by a divisor plate 34.
  • the height 37 with or without the load 35 put on points A, B, C and D has been measured in several tubs.
  • the comonomer content of the Component B is determined on the precipitated "amorphous" fraction of the polymer.
  • the precipitated "amorphous" fraction is obtained as follows: to one 100 ml aliquot of the filtered liquid obtained as described above (procedure for the Xylene-soluble faction) 200 ml of acetone are added under vigorous stirring. Precipitation must be complete as evidenced by a clear solid-solution separation. The solid thus obtained is filtered on a tared metallic screen and dried in a vacuum oven at 70°C until a constant weight is reached.
  • PI Polydispersity Index
  • modulus separation is defined as:
  • G' is the storage modulus and G" is the loss modulus.
  • the solid catalyst component described above is contacted at 12 °C for 24 minutes with aluminum triethyl (TEAL) and dicyclopentyldimethoxysilane (DCPMS).
  • TEAL aluminum triethyl
  • DCPMS dicyclopentyldimethoxysilane
  • the catalyst system is then subjected to prepolymerization by maintaining it in suspension in liquid propylene at 20 °C for about 5 minutes before introducing it into the first polymerization reactor.
  • the propylene polymer compositions of the examples were prepared in a two-step polymerization process, wherein the copolymer (A) was prepared in the first polymerization step by feeing the monomers and the catalyst system to a gas-phase polymerization reactor comprising two interconnected polymerization zones, a riser and a downcomer, as described in the European Patent EP1012195.
  • the polymerization mixture was discharged from said reactor, conveyed to a gas-solid separator and the polymerized material was sent into a conventional gas-phase fluidized-bed reactor where the ethylene/propylene copolymer (B) was produced.
  • the operative conditions are indicated in Table 1.
  • Component B gas phase reactor
  • the flask was heated to 40°C and 4.4 mmoles of diisobutylphthalate were thereupon added. The temperature was raised to 100 °C and maintained for two hours, then the stirring was discontinued, the solid product was allowed to settle and the supernatant liquid was siphoned off.
  • the catalyst component contained 2.8 wt% of Ti and 12.3 wt% of phthalate.
  • the solid catalyst component described above is contacted at 12 °C for 24 minutes with aluminum triethyl (TEAL) and dicyclopentyldimethoxysilane (DCPMS).
  • TEAL aluminum triethyl
  • DCPMS dicyclopentyldimethoxysilane
  • the catalyst system is then subjected to prepolymerization by maintaining it in suspension in liquid propylene at 20 °C for about 5 minutes before introducing it into the first polymerization reactor.
  • the polymerization run is conducted in continuous mode in a series of three reactors equipped with devices to transfer the product from one reactor to the one immediately next to it.
  • the first two reactors are liquid phase reactors, and the third is a fluid bed gas phase reactor.
  • Component (A) is prepared in the first and second reactor, while component (B) is prepared in the third.
  • Hydrogen is used as molecular weight regulator.
  • the gas phase (propylene, ethylene and hydrogen) is continuously analyzed via gas- chromatography.
  • the powder is discharged and dried under a nitrogen flow.
  • the polypropylene resin of example 2 and of comparative example 1 were injection molded to form a tub similar to that one described in figure 2.
  • a load test with a load of 4,5 kg to evaluate the stiffness of the product has been carried out. As described in figure 4, the test has been carried out by measuring the height 37 with or without the load 35 put on points A-D. several tubs haven been tested the results are show in table 4.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un procédé pour fabriquer une cuve fixe d'une machine à laver comprenant l'étape de moulage par injection d'une résine en polypropylène sous la forme de la cuve ; où la résine en polypropylène comprend (en pour cent en poids) : A) de 50 % à 90 % d'un polymère de propylène contenant de 0 à 5 % en poids de motifs dérivés d'éthylène, ayant une polydispersité (PI) dans la plage de 4,5 à 8,0 ; B) de 50 % à 10 % d'un copolymère de propylène-éthylène contenant de 25 % en poids à 60 % en poids de motifs dérivés d'éthylène.
PCT/EP2011/057471 2010-05-19 2011-05-10 Cuve en polypropylène pour machine à laver WO2011144486A1 (fr)

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CN201180024790.1A CN102884123B (zh) 2010-05-19 2011-05-10 用于洗涤机的聚丙烯桶

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EP10163284 2010-05-19
EP10163284.2 2010-05-19
US39643010P 2010-05-27 2010-05-27
US61/396,430 2010-05-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018214238B3 (de) 2018-08-23 2019-10-24 BSH Hausgeräte GmbH Dekorteil für ein wasserführendes Haushaltsgerät und wasserführendes Haushaltsgerät

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EP0045977A2 (fr) 1980-08-13 1982-02-17 Montedison S.p.A. Composants et catalyseurs pour la polymérisation d'oléfines
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
EP0361494A2 (fr) 1988-09-30 1990-04-04 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
EP0395083A2 (fr) 1989-04-28 1990-10-31 Montell North America Inc. Composant et catalyseur pour polymérisation d'oléfines
EP0728769A1 (fr) 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
WO1998044001A1 (fr) 1997-03-27 1998-10-08 Commonwealth Scientific And Industrial Research Organisation Reactifs polyvalents presentant une avidite elevee et une specificite multiple
EP1012195A1 (fr) 1998-07-08 2000-06-28 Montell Technology Company bv Procede et dispositif de polymerisation en phase gazeuse
WO2000063261A1 (fr) 1999-04-15 2000-10-26 Basell Technology Company B.V. Constituants et catalyseurs de polymerisation d'olefines
US6435366B1 (en) * 1999-08-12 2002-08-20 Maytag Corporation Appliance washing tub having non-metallic reinforcing body and metallic inner liner
EP1272533A1 (fr) 2000-10-13 2003-01-08 Basell Poliolefine Italia S.p.A. Constituants de catalyseur pour la polymerisation d'olefines
US20060086379A1 (en) 2004-10-26 2006-04-27 Maytag Corporation Flame treatment of washing machine parts
US20070203298A1 (en) * 2004-05-21 2007-08-30 Basell Poliolefine Italia S.R.L. Impact Resistant Polyolefin Compositions

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CN2174160Y (zh) * 1993-08-14 1994-08-17 郑荣 全塑餐具清洗机
CN100534754C (zh) * 2007-09-13 2009-09-02 广安市超臣实业有限公司 抗菌洗衣桶的生产方法及其产品

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Publication number Priority date Publication date Assignee Title
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
EP0045977A2 (fr) 1980-08-13 1982-02-17 Montedison S.p.A. Composants et catalyseurs pour la polymérisation d'oléfines
EP0361494A2 (fr) 1988-09-30 1990-04-04 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
EP0395083A2 (fr) 1989-04-28 1990-10-31 Montell North America Inc. Composant et catalyseur pour polymérisation d'oléfines
EP0728769A1 (fr) 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
WO1998044001A1 (fr) 1997-03-27 1998-10-08 Commonwealth Scientific And Industrial Research Organisation Reactifs polyvalents presentant une avidite elevee et une specificite multiple
EP1012195A1 (fr) 1998-07-08 2000-06-28 Montell Technology Company bv Procede et dispositif de polymerisation en phase gazeuse
WO2000063261A1 (fr) 1999-04-15 2000-10-26 Basell Technology Company B.V. Constituants et catalyseurs de polymerisation d'olefines
US6435366B1 (en) * 1999-08-12 2002-08-20 Maytag Corporation Appliance washing tub having non-metallic reinforcing body and metallic inner liner
US6716383B1 (en) 1999-08-12 2004-04-06 Maytag Corporation Method of forming an appliance washing tub having non-metallic reinforcing body and metallic inner liner
EP1272533A1 (fr) 2000-10-13 2003-01-08 Basell Poliolefine Italia S.p.A. Constituants de catalyseur pour la polymerisation d'olefines
US20070203298A1 (en) * 2004-05-21 2007-08-30 Basell Poliolefine Italia S.R.L. Impact Resistant Polyolefin Compositions
US20060086379A1 (en) 2004-10-26 2006-04-27 Maytag Corporation Flame treatment of washing machine parts

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018214238B3 (de) 2018-08-23 2019-10-24 BSH Hausgeräte GmbH Dekorteil für ein wasserführendes Haushaltsgerät und wasserführendes Haushaltsgerät

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CN102884123B (zh) 2015-03-25

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