WO2004005397A1 - Compositions polymeriques a base de polymeres vinylaromatiques resistants aux chocs - Google Patents

Compositions polymeriques a base de polymeres vinylaromatiques resistants aux chocs Download PDF

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Publication number
WO2004005397A1
WO2004005397A1 PCT/EP2003/006840 EP0306840W WO2004005397A1 WO 2004005397 A1 WO2004005397 A1 WO 2004005397A1 EP 0306840 W EP0306840 W EP 0306840W WO 2004005397 A1 WO2004005397 A1 WO 2004005397A1
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WO
WIPO (PCT)
Prior art keywords
vinyl aromatic
compositions according
weight
aromatic polymer
molecular weight
Prior art date
Application number
PCT/EP2003/006840
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English (en)
Inventor
Riccardo Po'
Giorgio Giannotta
Leonardo Castellani
Claudio Maestrini
Angelo Ferrando
Original Assignee
Polimeri Europa S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polimeri Europa S.P.A. filed Critical Polimeri Europa S.P.A.
Priority to AU2003253020A priority Critical patent/AU2003253020A1/en
Publication of WO2004005397A1 publication Critical patent/WO2004005397A1/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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to a composition based on impact resistant vinyl aromatic polymers.
  • compositions comprising an impact resistant vinyl aromatic polymer, a vinyl aromatic polymer having a predominantly syndiotactic structure and, possibly, a polyphenyl ether.
  • Compositions based on impact resistant vinyl aromatic polymers and vinyl aromatic polymers having a predominantly syndiotactic structure are known in literature.
  • US patent 6,169,146 describes polymeric compositions having an improved resistance to solvents, containing an atactic polystyrene, possibly impact resistant, in a quantity ranging from 30 to 95% by weight and a syndiotactic polystyrene having a melting point not higher than 255°C, in a quantity ranging from 5 to 70% by weight.
  • compositions of the known technique can contain, in addition to these two components, one or more of the following addi- tives selected from a polyphenylene ether, an inorganic filler and a polymer compatible with atactic or syndiotactic polystyrene, having a polar group in the chain.
  • compositions are prepared by kneading the components at a temperature ranging from the melting point of the syndiotactic polystyrene to 270°C.
  • compositions based on atactic or syndiotactic polystyrene with a high resistance to solvents starting from traditional products, i.e. from a product having a melting point of about 270°C, in the case of syndiotactic polymers.
  • these blends can also be advantageously prepared at temperatures lower than the melting points of the syndiotactic product.
  • the object of the present invention therefore relates to polymeric compositions comprising: a) 70-97% by weight, preferably 75-95%, of a vinyl aro- atic polymer modified with rubber; b) 3-30% by weight, preferably 5-25%, of a vinyl aromatic polymer having a predominantly syndiotactic structure with a melting point higher than 255°C; c) 0-10% by weight with respect to (a) + (b) , preferably 0.5-5%, of a polyphenylene ether having an intrinsic viscosity higher than or equal to 0.1 dl/g measured in chloroform at 25°C; d) 0-10% by weight with respect to (a) + (b) of an elastomer selected from block copolymers consisting of at least one polymeric non-elastomeric block of a vinyl aromatic monomer and at least one elastomeric block based on a 1, 3-conjugated diene, possibly hydrogenated, having the same or different molecular weight, where
  • vinyl aromatic polymer as used in the present description and claims for identifying both components (a) and (b) , essentially refers to a product obtained by the polymerization of at least one monomer having the fol- lowing general formula:
  • n is zero or an integer ranging from 1 to 5
  • R is a hydrogen atom or a methyl
  • Y is a halogen, such as chlorine or bromine, or an alkyl or alkoxyl radical having from 1 to 4 carbon atoms .
  • vinyl aromatic monomers having the above general formula are: styrene, ⁇ -methyl styrene, methyl sty- rene, ethyl styrene, butyl styrene, dimethyl styrene, mono-, di-, tri-, tetra- and penta-chloro styrene, bro o styrene, methoxy-styrene, acetoxy-styrene, etc.
  • Styrene and ⁇ -methyl styrene are the preferred vinyl aromatic monomers.
  • the vinyl aromatic monomers having general formula (I) can be used alone or mixed, up to 50% by weight, with other copolymerizable monomers. Examples of these monomers are
  • (meth) acrylic acid C1-C4 alkyl esters of (meth) acrylic acid, such as methacrylate, methyl methacrylate, ethyl ac- rylate, ethyl methacrylate, isopropyl acrylate, butyl ac- rylate, amides and nitriles of (meth) acrylic acid, such as acrylamide, methacrylamide, acrylonitrile, ethacryloni- trile, butadiene, ethylene, divinyl benzene, maleic anhydride, etc.
  • Preferred copolymerizable monomers are acrylonitrile and methyl methacrylate.
  • the vinyl aromatic polymer, or copoly er, (a) which is obtained has an average molecular weight Mw ranging from 50,000 to 1,000,000, preferably from 70,000 to 300,000.
  • the vinyl aromatic polymer of step (a) comprises a polymeric matrix wherein a rubber-like phase is dispersed, or grafted, in the form of substantially spherical particles, having an average diameter of between 0.1 and 2 ⁇ m, preferably between 0.2 and 1.2 ⁇ m, in a quantity ranging from 4 and 15% by weight with respect to the total of component (a) .
  • the rubber-like phase can be selected from di- ene rubbers (i) and/or from block copolymers (ii) consist- ing of at least one non-elastomeric polymeric block of a vinyl aromatic monomer and at least one elastomeric block based on a 1, 3-conjugated diene, having the same or different molecular weight, wherein the diene content is equal to or higher than 50% by weight, preferably between 50 and 90%.
  • Further rubbers which can be used as rubber-like phase dispersed in the polymeric matrix are low unsaturated rubbers (iii), such as ethylene/propylene (EPR) or ethylene- propylene-diene (EPDM) rubbers.
  • the diene rubbers are usually of the synthetic type consisting, in particular, of a polymer of a 1, 3-conjugated diene containing from 4 to 6 carbon atoms. Examples of these rubbers are polybutadiene and polyisoprene.
  • Polybuta- diene is particularly preferred, having: - a Mooney viscosity ranging from 20 to 70 ML 1+4 at 100°C, measured according to the ASTM D 1646-80 standard method; a viscosity in solution ranging from 40 to 200 cps measured in a solution at 5% by weight in styrene at 25°C; a 1,2 vinyl content ranging from 5 to 35% wt; and a content of 1,4-cis ranging from 20 to 85% by weight.
  • the block copolymers (ii) are, for example, of the type: S-B; S ⁇ -B-S 2 ; B,-S-B 2 -S 2 ; wherein S, Si and S 2 represent non-elastomeric polymeric blocks having an average molecular weight Mw ranging from 5,000 to 250,000, whereas B, Bi e B 2 are elastomeric blocks based on a conjugated diene having an average molecular weight Mw ranging from 2.000 to 250,000.
  • Particularly preferred block copolymers are those having: a Mooney viscosity ranging from 25 to 50 ML 1+4 at 100°C, measured according to the ASTM D 1646-80 standard method; a viscosity in solution ranging from 25 to 60 cps, measured in solution at 5% by weight in styrene at 25°C; and wherein the polymeric, non-elastomeric block is polystyrene; and the 1, 3-conjugated diene used for the preparation of the elastomeric polymeric block is selected from those having from 4 to 8 carbon atoms. Examples of these dienes are: 1, 3-butadiene, isoprene, 2, 3-dimethyl-l, 3-butadiene, piperylene and mixtures thereof.
  • the vinyl aromatic polymer having a predominantly syn- diotactic structure has a melting temperature of about 265- 270°C, an average molecular weight Mw higher than 20,000, generally between 50,000 and 500,000, and a stereo regularity of the syndiotactic type higher than 90%, generally between 95 and 100%.
  • These polymers can be obtained by means of well-known processes described in literature.
  • Syndiotactic vinyl aromatic polymers having the above characteristics can be prepared, for example, by means of a catalytic system based on organo etallic complexes of titanium activated by alkyl alumoxanes or fluorinated derivatives of bo- ron, possibly in the presence of alkyl metals as described in US patent 4,680,353 and in the European patent 421,659 or in the US patents 5,629,391, 5,728,784, 5,830,959 and 6,174,973-
  • the polyphenylene ether used to prepare the polymeric compositions object of the present invention is a well known polymer or co-polymer widely used in industry, especially as engineering polymer, in applications in which impact strength and thermal resistance are required.
  • Polyphenylene ethers are polymers and co-polymers which comprise several structural units having general formula (II) :
  • -Ar-O- (II) wherein -Ar- represents an arylenic radical possibly substituted with one or more halogen atoms, one or more (iso) alkyl or (iso) alkoxyl radicals containing from 1 to 4 carbon atoms, one or more phenyls.
  • Preferred polyphenylene ethers according to the present invention are those having the following general formula (III) :
  • Ri radicals independently represent a C1-C4 (iso) alkyl or (iso) alkoxyl radical and m is an integer higher than 50, preferably between 60 and 600.
  • polyphenylene ethers particularly suitable for the present invention are: poly (2, 6-dimethyl-l, 4-phenylene) ether; - poly (2, 6-diethyl-l, 4-phenylene) ether; poly (2-methyl-6-ethyl-l, 4-phenylene) ether; poly (2, 6-diprophyl-l, 4-phenylene) ether
  • Poly (2, 6-dimethyl-l, 4-phenylene) ether is the preferred polyphenylene ether.
  • These polyphenylene ethers generally have an average molecular weight Mw, determined by means of Gel Permeation Chromatography, ranging from 5,000 to 120,000 and their intrinsic viscosity is higher than 0.1 dl/g, preferably between 0.3 and 0.9 dl/g.
  • the polyphenylene ethers used in the composition ob- ject of the present invention can be prepared by the oxidation of a phenolic compound with oxygen, or a gas contain ⁇ ing oxygen, preferably in the presence of a catalyst for oxidative coupling, as described in US patents 3,226,361, 3,234,183, 3,306,874, 3,257,357, 3,337,501, 3,956,242, 3,965,069, 4,075,174, 4,102,865, 4,184,034, 4,385,168.
  • elastomers (ii), optionally partially hydrogen- ated, used in combination with the vinyl aromatic polymer modified with rubber, described under item (a) can be used as elastomers (d) .
  • compositions object of the present invention can also contain, in addition to components (a) , (b) , (c) and (d) , reinforcing additives, such as, for example, glass fibers, carbon fibers, high modulus organic or inorganic fi- bers, inorganic fillers, flame retardant agents, nucleating agents, dyes, pigments, stabilizers, lubricants, etc. which are well known to technical experts in the field.
  • reinforcing additives such as, for example, glass fibers, carbon fibers, high modulus organic or inorganic fi- bers, inorganic fillers, flame retardant agents, nucleating agents, dyes, pigments, stabilizers, lubricants, etc. which are well known to technical experts in the field.
  • the reinforcing additives can generally be used in amounts not higher than 50% by weight, preferably not higher than 30%, with respect to the total composition.
  • Stabilizers suitable for being used in the compositions of the present invention include a large number of the known thermal stabilizers and oxidation stabilizers used for polyphenylene ether resins or vinyl aromatic poly- mers.
  • Liquid phosphates, for example, and sterically hin- dered phenols can be added to the compositions of the present invention in a quantity varying from 0.05 to 5% by weight.
  • compositions object of the present invention can be prepared with any conventional kneading method.
  • the preparation temperature of the mixture can be maintained, for example, at between 180°C and 300°C or, more preferably, between 180°C and 5°C below the melting point of the vinyl aromatic polymer having a predominantly syndiotactic structure (b) .
  • Any kneading unit can be used, operating in continuous or batchwise, such as, for example, twin- or single-screw mixers or extruders.
  • the kneading can be carried out in a number of steps as desired, for example by pre-mixing components (a) and (c) and then adding (b) ; or pre-mixing (b) , (c) and (d) and then adding (a) , and so on.
  • compositions, object of the present invention are used in the fields of motor vehicles, household appliances (for example television sets, refrigerators, air conditioners), for the production of manufactured products which must be oven-painted, parts in contact with engines, household appliances, electronic and technical articles, in the form of cups, boxes, containers, panels, sheets, bars, etc..
  • household appliances for example television sets, refrigerators, air conditioners
  • parts in contact with engines, household appliances, electronic and technical articles in the form of cups, boxes, containers, panels, sheets, bars, etc.
  • Impact resistant atactic polystyrene commercial product Edistir RR 745 (Poli eri Europa) ;
  • SEBS block styrene-hydrogenated butadiene elastomer
  • Kraton G 1652 Kraton Polymers
  • Poly (2, 6-dimethyl-l, -phenylene ether) commercial product PPO H 51 (Mitsubishi) .
  • the mechanical properties were determined according to ISO 180 (Izod Impact Strength) and ISO 527 (Tensile Test) on ISO 3167 injection molded test samples.
  • the resistance to solvents (ESCR, Environmental Stress-Cracking Resistance) was determined on the same test samples according to two different procedures. 1) Blistering tests The procedure used contemplates the deposition, by means of a pipette, of 1 to 6 drops of cyclopentane in several numbered positions (from 1 to 6) , at a frequency of 1 drop per minute. The samples are placed in an oven at 60°C for 15 minutes in order to release the cyclopentane penetrated.
  • the materials are compared, and the sample which starts forming blisters at the highest number of drops, is considered as being the best, using a parameter obtained by the sum of the number corresponding to the position in which corrosion of the test sample surface is observed and of that corresponding to complete blisters: the value of 7 corresponds to "no effect observed". Consequently, the values which represent solvent resistance range from 2 (very poor resistance) to 14 (perfect resistance) . Repeated tests confirmed the good reproducibility of the method. 2) ESCR tests
  • test samples of each specimen are clamped in a vice which bends them under flexion so that the external surface reaches a deformation level equal to 0.7%.
  • a drop of cyclo- pentane is dripped every 5 minutes onto this surface in a central position with respect to the length of the test sample.
  • the test samples are extracted from the vice and subjected to tensile stress according to ISO 527.
  • a blend based on 4,500 g of Edistir RR745 impact resistant polystyrene and 500 g of syndiotactic polystyrene was prepared in a Berstorff ZE 25 twin-screw extruder.
  • the temperature profile in the nine zones of the extruder was the following: 200-220-240-250-260-260-260-260-250°C. Comparative example
  • Example 1 was repeated, but using Edistir 1782 atactic polystyrene instead of 500 g of syndiotactic polystyrene.
  • Example 2 was repeated, but using Edistir 1782 atactic polystyrene instead of 500 g of syndiotactic polystyrene.
  • Example 1 was repeated, but using the following temperature profile of the extruder: 210-245-265-275-285-285-285-285-275°C.
  • Example 3 Example 2 was repeated, but using 3, 600 g of Edistir RR745 impact resistant polystyrene and 900 g of syndiotactic polystyrene.
  • Example 4 Example 1 was repeated, but using 4,350 g of Edistir RR745 impact resistant polystyrene, 250 g of Kraton G1652 (block styrene-hydrogenated butadiene elastomer) , 400 g of syndiotactic polystyrene.
  • Example 5 Example 1 was repeated, but using 4,350 g of Edistir RR745 impact resistant polystyrene, 200 g of PPO H 51, 400 g of syndiotactic polystyrene and 50 g of aluminum tert- butyl benzoate.
  • Example 6 Example 2 was repeated, but using 4,350 g of Edistir RR745 impact resistant polystyrene, 250 g of Kraton G1652, 400 g of syndiotactic polystyrene.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions polymériques contenant: a) 70 à 97 % en poids d'un polymère vinylaromatique modifié par caoutchouc; b) 3 à 30 % en poids d'un polymère vinylaromatique présentant une structure syndiotactique dont le point de fusion est supérieur à 255 °C; c) 0 à 10 % en poids, relativement aux proportions a) + b), d'un poly(phénylène éther); et d) 0 à 10 % en poids, relativement aux proportions a) + b), d'un élastomère choisi parmi des copolymères séquencés constitués d'au moins un bloc polymérique non élastomère d'un monomère vinylaromatique et d'au moins un bloc élastomère basé sur un diène 1,3-conjugué.
PCT/EP2003/006840 2002-07-09 2003-06-26 Compositions polymeriques a base de polymeres vinylaromatiques resistants aux chocs WO2004005397A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003253020A AU2003253020A1 (en) 2002-07-09 2003-06-26 Polymeric compositions based on impact resistant vinyl aromatic polymers.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2002MI001496A ITMI20021496A1 (it) 2002-07-09 2002-07-09 Composizioni polimeriche a base di polimeri vinilaromatici antiurto
ITMI2002A001496 2002-07-09

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WO2004005397A1 true WO2004005397A1 (fr) 2004-01-15

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WO (1) WO2004005397A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7906576B2 (en) * 2003-07-11 2011-03-15 Polimeri Europa S.P.A. Rubber-reinforced vinyl aromatic polymers
US9630851B2 (en) 2009-03-20 2017-04-25 Schlumberger Technology Corporation Derivatisation of carbon
US9804123B2 (en) 2008-07-03 2017-10-31 Schlumberger Technology Corporation Electrochemical sensor utilising a dual redox system contained within a single molecule

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EP0933393A1 (fr) * 1998-01-29 1999-08-04 Idemitsu Petrochemical Co., Ltd. Composition de résine de styrène et procédé pour la fabriquer, et procédé de préparation des produits moulés de résine de styrène
WO2001025329A1 (fr) * 1999-10-05 2001-04-12 Idemitsu Petrochemical Co., Ltd. Matiere a mouler, procede de production d'article moule et article moule
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WO2002077098A1 (fr) * 2001-03-23 2002-10-03 Idemitsu Petrochemical Co., Ltd. Composition de polymère de styrène et article moulé en cette matière
WO2002098960A1 (fr) * 2001-05-30 2002-12-12 Idemitsu Petrochemical Co., Ltd. Composition de resine de polystyrene resistant aux agents chimiques et article moule

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EP0933393A1 (fr) * 1998-01-29 1999-08-04 Idemitsu Petrochemical Co., Ltd. Composition de résine de styrène et procédé pour la fabriquer, et procédé de préparation des produits moulés de résine de styrène
WO2001025329A1 (fr) * 1999-10-05 2001-04-12 Idemitsu Petrochemical Co., Ltd. Matiere a mouler, procede de production d'article moule et article moule
JP2002113756A (ja) * 2000-10-05 2002-04-16 Idemitsu Petrochem Co Ltd 透明スチレン系樹脂成形体の製造方法及び透明スチレン系樹脂成形体
WO2002077098A1 (fr) * 2001-03-23 2002-10-03 Idemitsu Petrochemical Co., Ltd. Composition de polymère de styrène et article moulé en cette matière
WO2002098960A1 (fr) * 2001-05-30 2002-12-12 Idemitsu Petrochemical Co., Ltd. Composition de resine de polystyrene resistant aux agents chimiques et article moule

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7906576B2 (en) * 2003-07-11 2011-03-15 Polimeri Europa S.P.A. Rubber-reinforced vinyl aromatic polymers
US9804123B2 (en) 2008-07-03 2017-10-31 Schlumberger Technology Corporation Electrochemical sensor utilising a dual redox system contained within a single molecule
US9630851B2 (en) 2009-03-20 2017-04-25 Schlumberger Technology Corporation Derivatisation of carbon
US10407379B2 (en) 2009-03-20 2019-09-10 Schlumberger Technology Corporation Derivatisation of carbon

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ITMI20021496A1 (it) 2004-01-09
AU2003253020A1 (en) 2004-01-23

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