GB2118194A - Polymeric blends based on vinyl-aromatic polymers - Google Patents

Polymeric blends based on vinyl-aromatic polymers Download PDF

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Publication number
GB2118194A
GB2118194A GB08308155A GB8308155A GB2118194A GB 2118194 A GB2118194 A GB 2118194A GB 08308155 A GB08308155 A GB 08308155A GB 8308155 A GB8308155 A GB 8308155A GB 2118194 A GB2118194 A GB 2118194A
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United Kingdom
Prior art keywords
aromatic
weight
carbon atoms
vinyl
polymeric blend
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GB08308155A
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GB8308155D0 (en
GB2118194B (en
Inventor
Gianfranco Biglione
Gian Claudio Fasulo
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Montedison SpA
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Montedison SpA
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Publication of GB2118194A publication Critical patent/GB2118194A/en
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Publication of GB2118194B publication Critical patent/GB2118194B/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions 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
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/12Copolymers of styrene with unsaturated nitriles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates

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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

Polymeric blends comprise 20-80% by weight of a modified vinyl-aromatic polymer containing from 5 to 15% by weight of an ethylenically unsaturated nitrile, and 80-20% by weight of at least one resin containing aromatic groups selected from certain defined aromatic polycarbonates and certain defined crystalline aromatic polyesters.

Description

SPECIFICATION Polymeric blends based on vinyl-aromatic polymers The present invention relates to polymeric blends based on vinyl-aromatic polymers, and more particularly to blends which contains an alkenyl-aromatic resin and are suitable to be transformed into shaped articles by injection moulding extrusion or other known processing techniques for thermoplastic polymers.
From British Patent Application No. 2 067 579 A are known vinyl-aromatic polymers which possess an improved stress cracking resistance and are particularly suitable to be moulded or vacuum shaped.
These vinyl-aromatic polymers modified with rubber are characterized in that they contain from 6 to 12% by weight of an ethylenically unsaturated nitrile, such as acrylonitrile, bound to the two phase system of the polymer, and exhibit the following particular combination of characteristics: (a) the dispersed elastomeric gel phase insoluble in toluene is not less than 23% by weight; (b) the swelling index of the elastomeric phase in toluene is greater than 10; (c) the melt index of the.polymer is at least 1.5 g./1 0 min.; (d) the bending modulus of the polymer is greater than 1 5,000 kg/cm2; (e) the torsional modulus of the polymer is greater than 5,500 kg/cm2; (f) the notched IZOD impact strength at230Cofthe polymer is greater than 7 kg.cm/cm.
The methods of measuring the above-mentioned characteristics are described in the Patent Application No. 2 067 5i9A.
Such modified vinyl-aromatic polymers are particularly suitable to be used in the production both of refrigerator cells and of other articles obtained by thermoforming the extruded sheets. Such polymers can be easily manufactured by processes which are presently in use. Furthermore, they are compatible both with polystyrol or impact resistant polystyrol, as well as with ABS thermopolymers and styrol/acrylonitrile copolymers (SAN).
Nevertheless, these vinyl-aromatic polymers modified with an ethylenically unsaturated nitrile, and also in general all vinyl-aromatic polymers, have the drawback of having a low heat distorsion temperature so that their thermal resistance is not sufficiently satisfactory to meet the necessary requirements in some fields of application, for example in the automotive industry.
The present invention aims to improve the thermal resistance of vinyl-aromatic polymers modified with an ethylenically unsaturated nitrile, without altering and preferably improving their chemicalphysical properties.
According to the present invention, there is provided a polymeric blend containing: -from 20 to 80% by weight, with respect to the blend, of a modified vinyl-aromatic polymer container from 5 to 1 5% by weight of an ethylenically unsaturated nitrile; -from 80 to 20% by weight, with respect to the blend, of at least one resin containing aromatic groups selected from: (a) an aromatic polycarbonate having repeating structural units of the formula::
in which R1, R2, R3 and R4 each represents hydrogen or an alkyl radical containing from 1 to 3 carbon atoms, and A represents -0-, -CO-, SO2, an a Ikylene radical containing from 1 to 10 carbon atoms, an alkylidene radical containing from 1 to 10 carbon atoms, a cyclo-alkylene radical containing from 5 to 15 carbon atoms, a cyclo-alkylidene radical containing from 5 to 15 carbon atoms or the radical:
and (b) a crystalline aromatic polyester obtained by polymerization of a glycol of general formula: HO-(CH2)n-OH (II) in which n is an integer from 2 to 10, with a bicarboxylic acid of formula:: HOOC-R5-B-R6-COOH (III) in which R5 and R6 each represents (CH2) where m is zero or an integer from 1 to 4 and B is a bivalent aromatic radical represented by:
in which D may be: -(CH2)-; -(CH2)0-(CH2)-; (CH2)pO(CH2) -; (CH2)q
where p may be zero or an integer from 1 to 5 and q is an integer from 1 to 5.
The term vinyl-aromatic polymer as used herein is to be understood to include any solid thermoplastic polymer and respective copolymer, essentially consisting of (i.e. containing chemically bound) at least 50% by weight of one or more vinyi-aromatic compounds of general formula:
in which X represents hydrogen or an alkyl radical having from 1 to 4 carbon atoms; Y represents hydrogen, a halogen or an alkyl radical having from 1 to 4 carbon atoms; and n is zero or an integer from 1 to 5.
Examples of vinyl-aromatic compounds having the formula (IV) are: styrene; methyl styrene; mono-, di-, tri-, tetra-, and penta-chloro-styrene and the respective alpha-methyl-styrenes; styrenes alkylated in the nucleus and the respective alpha-methyl-styrenes such as ortho- and para-methylstyrenes and ortho- and para-ethyl-styrenes; and ortho- and para-alpha-methyl-styrenes. These monomers may be used alone or in admixture with each other.
The term vinyl-aromatic polymers also includes polystyrenes modified with rubbers, which are generally employed to render the polymers impact-resistant.
The rubbers which are generally used for this purpose are polybutadiene, polyisoprene, copolymers of butadiene and/or of isoprene with styrene or with other monomers, having a glass transition temperature (Tg) lower than -200C, or the saturated rubbers such as ethylene-propylene rubbers, ethylene-propylene-diene terpolymers, and siliconic rubbers with unsaturated groups.
The vinyi-aromatic polymers contain from 5 to 15%, and preferably less than "r 10% by weight, of an ethylenically unsaturated nitrile such as acrylonitrile or methacrylonitrile.
The aromatic polycarbonates containing the repeating structural units (I) are well known in the art and are commercially available from different sources, for example General Eiectric Company, Pittsfield, Mass., USA under the Trade Mark "LEXAN"; or from ANIC of S. Donato Milanese, Milan, Italy under the Trade Mark "SINVET".
Generally any aromatic polycarbonate may be used; however those obtained from bisphenol A are particularly preferred. Thegolycarbonates employed in the composition of the present invention suitably have a molecular weight Mw ranging from 10,000 to over 200,000, more preferably from 20,000 to 60,000.
The crystalline polyesters are well known in the art and are commercially available from different sources.
Representative examples of crystalline polyesters obtained by polymerization of a glycol (II) with a bicarboxylic acid (III) are: polyethylene-terephthalate, polybutene-terephthalate, and polyethylene-2,2' di-phenoxy-ethane-4,4'-dicarboxyl ate.
These crystalline polyesters preferably have a molecular weight ranging from 10,000 to 60,000.
The polymeric blends of the present invention can be prepared in different ways, for example by single screw or double-screw extrusion and subsequent granulation, or by mastication in a Banbury mixer and subsequent cube shaping by means of a calender.
To the blends may be added optional additives such as antistatic agents, flame proofing agents, lubricating agents, colouring agents, physical and chemical expanding agents such as Freon, pentane,or azodicarbonamide.The blend can bye also reinforced by glass fibres or synthetic fibres. "FREON" is a Registered Trade Mark.
The invention will be further described with reference to the following illustrative Examples. In the Examples all the parts are expressed by weight, unless indicated otherwise.
The properties of the blends of the present invention have been tested on test pieces moulded by injection, by using the following methods: 1. The heat distortion temperature (HDT) was determined according to the standard ASTM D 648, at 66 psi and at 264 psi.
2. The Vicat softening point procedure A was determined according to the standard ASTM D 1 525.
3. ThelZOD impact strength was determined at 230C according to the standard ASTM D 256, by using test pieces of size 1/2" x -1/8" (1.27 cm x 0.32 cm).
4. The tests for the resistance against Freon (ESC) were carried out on test pieces subjected to creep in a tensile test, maintaining their central part, for a 40 mm stretch, in contact with liquid Freon 11. For this purpose, a glass container containing Freon 11 was fixed, by means of a rubber gasket, to.
the lower end of the vertically arranged test piece, in correspondence with its wider stretch. The test piece was subjected to a load'of 100 Kg/cm2 and the time~necessary for the rupture of the same was measured.
EXAMPLES 1-4 By means of a single screw extruder BANTER A TR 45, having a length/diameter ratio = 30, there were extruded with degasification and at the temperature.given in Table I, blends consisting of: -a modified vinyl-aromatic polymer having the following composition: 72% by weight of styrene, 123% by weight of alpha-methyl-styrene, 8% by weight, of acrylonitrile and 8% by weight of rubber; -an aromatic polycarbonate, "SINVET 221", sold by ANIC of S. Donato Milanese, Milan, Italy, in the amount given in Table I; and 0.05% by weight of a sterically hindered phenolic antioxidant, IRGANOX 1076.
By cutting'the filaments coming from the extruder, granules were obtained which were dried at 900C for two hours. The granules were moulded by injection, at a temperature that was 200C higher than the lowest filling temperature of the mould impression, on a NEGRI 8 BOSSY V-i 7-110 FA press, and thus test pieces were obtained.
The properties of the thus obtained test pieces are given in the following Table I.
TABLE I
Example No. 1 2 3 4 Vinyl-aromatic polymer 100 -70 50 30 Polycarbonate "SINVET" parts by weight) 0 30 50 70 Extrusion temperature of the blend (OC) 210 250 250 260 Lowest filling temperature of the mould impression 190 220 240 260 for injection of the test pieces (OC) HDTat 66psi(OC) 97 107 115 125 at 265 psi (OC) 89 96 105 119 VICAT A at 1 kg. in oil (OC) 107 118 129 140 at 5 kg. in oil(OC) 98 108 119 130 IZOD impact strength (J/m) 70 250 400 590 E.S.C. in Freon 11 (hours) 2 20 50 70 EXAMPLES 5--8 Following the procedures of Example 1 , test pieces were prepared by using blends consisting of: -a modified vinyl-aromatic polymer consisting of 84% by weight of styrene, 8% by weight of acrylonitrile, and 8% by weight of rubber; and -an amount given in Table ll of a polybutyleneterephthalate, "PIBITER N 100", of the present Applicants.
The properties of the obtained test pieces are given in Table II.
TABLE ll
Example No. 5 6 7 8 Vinyl-aromatic polymer 100 75 50 25 Polybutyleneterephthalate "PIBITER N 100" 0 25 50 75 (parts by weight) Extrusion temperature of the blend (OC) 200 230 230 240 Lowest filling temperature of the mould impression 175 195 220 225 for injection of the test pieces (OC) HDTat 66psi(OC) 94 95 94 105 at 264 psi (OC) 84 83 79 72 VICAT A at 1 kg. in oil (OC) 90 92 99 126 at 5 kg. in oil (OC) IZOD impact strength (J/m) 80 49 50 55 E.S.C. in Freon 11 (hours) 1 20 150 170

Claims (8)

1. A polymeric blend containing: -from 20 to 80% by weight, with respect to the blend, of a modified vinyl-aromatic polymer container from 5 to 15% by weight of an ethylenically unsaturated nitrile; -from 80 to 20% by weight, with respect to the blend, of at least one resin containing aromatic groups selected from: (a) an aromatic polycarbonate having repeating structural units of the formula::
in which R1, R2, R3 and R4 each represents hydrogen or an alkyl radical containing from 1 to 3 carbon atoms, and A represents -0-, -CO-, S02, an alkylene radical containing from 1 to 10 carbon atoms, an alkylidene radical containing from 1 to 10 carbon atoms, a cyclo-alkylene radical containing from 5 to 1 5 carbon atoms, a cyclo-alkylidene radical containing from 5 to 1 5 carbon atoms or the radical:
and (b) a crystalline aromatic polyester obtained by polymerization of a glycol of general formula: HO(CH2)nOH (II) in which n is an integer from 2 to 10, with a bicarboxylic acid of formula:: H0OC-R-B-R6OOH (Ill) in which R5 and R6 each represents (CH2)rn where m is zero or an integer from 1 to 4 and B is a bivalent aromatic radical represented by:
in which D may be: -(CH2)p-;-(CH2)p-COCH2)p-; -(CH2)p-(CH2)-;-O-(CH2)q-O-;
where p may be zero or an integer from 1 to 5 and q is an integer from 1 to 5.
2. A polymeric blend as claimed in Claim 1, in which the modified vinyl-aromatic polymer contains at least 50% by weight of one or more vinyl-aromatic compounds of general formula:
in which X represents hydrogen or an alkyl radical having from 1 to 4 carbon atoms; Y represents hydrogen, a halogen, or an alkyl radical having from 1 to 4 carbon atoms; and n is zero or an integer from 1 to 5.
3. A polymeric blend as claimed in Claim 1 or 2, in which the vinyl-aromatic polymer contains rubber, to render the polymer impact-resistant.
4. A polymeric blend as claimed in any of Claims 1 to 3, in which the ethylenically unsaturated nitrile is acrylonitrile.
5. A polymeric blend as claimed in any of Claims 1 to 4, in which the content of ethylenically unsaturated nitrile in the modified vinyl-aromatic polymer is less than 10% by weight.
6. A polymeric blend as claimed in any of Claims 1 to 5, in which the polycarbonate is obtained from bisphenol.
7. A polymeric blend as claimed in any of Claims 1 to 6, in which the aromatic polyester is polybutylene-terephthalate,
8. A polymeric blend according to Claim 1, as described in any of the foregoing Examples.
GB08308155A 1982-03-24 1983-03-24 Polymeric blends based on vinyl-aromatic polymers Expired GB2118194B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT20362/82A IT1199981B (en) 1982-03-24 1982-03-24 MIXTURES BASED ON VINYL-AROMATIC POLYMERS

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GB8308155D0 GB8308155D0 (en) 1983-05-05
GB2118194A true GB2118194A (en) 1983-10-26
GB2118194B GB2118194B (en) 1986-04-03

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GB08308155A Expired GB2118194B (en) 1982-03-24 1983-03-24 Polymeric blends based on vinyl-aromatic polymers

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DE (1) DE3310757A1 (en)
ES (1) ES520894A0 (en)
FR (1) FR2523988B1 (en)
GB (1) GB2118194B (en)
IT (1) IT1199981B (en)
NL (1) NL8301006A (en)
SE (1) SE455199B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0146023A1 (en) * 1983-12-07 1985-06-26 Bayer Ag Use of halogene-free polycarbonates based on bis (3,5-dimethyl-4-hydroxyphenyl)-methane in combination with polymers as fire retardants
EP0146021A1 (en) * 1983-12-07 1985-06-26 Bayer Ag Process for the preparation and/or working-up of polymer mixtures
DE3603185A1 (en) * 1985-02-08 1986-08-14 GE Plastics ABS Europe B.V., Amsterdam THERMOPLASTIC COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND ITEMS OBTAINED FROM THEM
EP0277835A2 (en) * 1987-02-04 1988-08-10 ENICHEM S.p.A. Blends based on vinyl-aromatic polymers with improved characteristics of chemical resistance

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007006776A1 (en) 2007-02-12 2008-08-21 Dracowo Forschungs- Und Entwicklungs Gmbh Polymer network with adjustable gel time and good mechanical and thermal properties, is obtained by mixing unsaturated polyester and natural epoxy resins

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB991422A (en) * 1961-03-24 1965-05-05 Borg Warner Improvements in or relating to synthetic resin compositions
GB1418244A (en) * 1973-05-04 1975-12-17 Bayer Ag Thermoplastic moulding compositions
GB1440783A (en) * 1972-08-30 1976-06-23 Teijin Ltd Thermoplastic resin composition
GB1449870A (en) * 1973-06-09 1976-09-15 Bayer Ag Transparent moulding compositions
GB1452141A (en) * 1973-06-09 1976-10-13 Bayer Ag Polycarbonate moulding compositions
US4148956A (en) * 1976-12-31 1979-04-10 Alkor Gmbh Thermoplastic moulding composition and its use and sheets made from the moulding composition
GB1578380A (en) * 1976-11-23 1980-11-05 Bayer Ag Thermoplastic polycarbonate moulding compositions
GB1578384A (en) * 1976-11-23 1980-11-05 Bayer Ag Thermoplastic polycarbonate moulding compositions

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5145306B2 (en) * 1973-10-13 1976-12-03
DE2717165A1 (en) * 1977-04-19 1978-11-02 Bayer Ag THERMOPLASTIC MOLDING COMPOUNDS MADE FROM POLYCARBONATE AND ABS POLYMERIZED
DE2927576A1 (en) * 1979-07-07 1981-01-15 Bayer Ag HIGH IMPACT POLYBUTYLENE TEREPHTHALATE
DE3344102A1 (en) * 1983-12-07 1985-06-13 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING AND / OR PROCESSING POLYMER MIXTURES

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB991422A (en) * 1961-03-24 1965-05-05 Borg Warner Improvements in or relating to synthetic resin compositions
GB1440783A (en) * 1972-08-30 1976-06-23 Teijin Ltd Thermoplastic resin composition
GB1418244A (en) * 1973-05-04 1975-12-17 Bayer Ag Thermoplastic moulding compositions
GB1449870A (en) * 1973-06-09 1976-09-15 Bayer Ag Transparent moulding compositions
GB1452141A (en) * 1973-06-09 1976-10-13 Bayer Ag Polycarbonate moulding compositions
GB1578380A (en) * 1976-11-23 1980-11-05 Bayer Ag Thermoplastic polycarbonate moulding compositions
GB1578384A (en) * 1976-11-23 1980-11-05 Bayer Ag Thermoplastic polycarbonate moulding compositions
US4148956A (en) * 1976-12-31 1979-04-10 Alkor Gmbh Thermoplastic moulding composition and its use and sheets made from the moulding composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0146023A1 (en) * 1983-12-07 1985-06-26 Bayer Ag Use of halogene-free polycarbonates based on bis (3,5-dimethyl-4-hydroxyphenyl)-methane in combination with polymers as fire retardants
EP0146021A1 (en) * 1983-12-07 1985-06-26 Bayer Ag Process for the preparation and/or working-up of polymer mixtures
US4564654A (en) * 1983-12-07 1986-01-14 Bayer Aktiengesellschaft Process for the preparation and/or further processing of polymer blends
DE3603185A1 (en) * 1985-02-08 1986-08-14 GE Plastics ABS Europe B.V., Amsterdam THERMOPLASTIC COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND ITEMS OBTAINED FROM THEM
FR2577230A1 (en) * 1985-02-08 1986-08-14 Charbonnages Ste Chimique NOVEL COMPOSITIONS OF POLYMER RESINS BASED ON ACRYLONITRILE-BUTADIENE-STYRENE WITH IMPROVED PROPERTIES
EP0277835A2 (en) * 1987-02-04 1988-08-10 ENICHEM S.p.A. Blends based on vinyl-aromatic polymers with improved characteristics of chemical resistance
EP0277835A3 (en) * 1987-02-04 1989-08-09 Montedipe S.P.A. Blends based on vinyl-aromatic polymers with improved characteristics of chemical resistance

Also Published As

Publication number Publication date
ES8504886A1 (en) 1985-05-01
GB8308155D0 (en) 1983-05-05
FR2523988A1 (en) 1983-09-30
ES520894A0 (en) 1985-05-01
SE455199B (en) 1988-06-27
IT1199981B (en) 1989-01-05
NL8301006A (en) 1983-10-17
FR2523988B1 (en) 1986-01-03
IT8220362A0 (en) 1982-03-24
GB2118194B (en) 1986-04-03
DE3310757A1 (en) 1983-09-29
SE8301516D0 (en) 1983-03-21
SE8301516L (en) 1983-09-25

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