EP0765362A1 - POLYMERES SEQUENCES STYRENE-BUTADIENE STABILISES PAR $g(a)-TOCOPHEROL - Google Patents
POLYMERES SEQUENCES STYRENE-BUTADIENE STABILISES PAR $g(a)-TOCOPHEROLInfo
- Publication number
- EP0765362A1 EP0765362A1 EP95923266A EP95923266A EP0765362A1 EP 0765362 A1 EP0765362 A1 EP 0765362A1 EP 95923266 A EP95923266 A EP 95923266A EP 95923266 A EP95923266 A EP 95923266A EP 0765362 A1 EP0765362 A1 EP 0765362A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- block
- molecular weight
- styrene
- mol
- weight
- Prior art date
- Legal status (The legal status 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 status listed.)
- Ceased
Links
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
Definitions
- polymeric materials are subject to signs of aging, which have an undesirable effect during manufacture, storage, processing or use and are caused in the broadest sense by oxidation.
- the olefinically unsaturated polymers formed by polymerizing dienes, such as natural or synthetic rubber or thermoplastics toughened with such polymers, are particularly sensitive.
- the polymers change their external appearance (loss of transparency, yellowing, cracking, etc.) and more or less in parallel lose their good mechanical properties (impact resistance, elongation at break, tensile strength). In extreme cases, a commodity becomes completely unusable.
- antioxidants are chemical compounds which can delay the oxidation and the resulting aging phenomena of a polymer, whereby they are typically changed themselves. They are generally effective even in small amounts and are expediently added to a polymer as early as possible (R. Gumbleter and H. Müller, Taschenbuch der Kunststoff-Additive, 2nd edition, 1983, p. 2, Carl Hanser Verlag Kunststoff) .
- ABS acrylonitrile-butadiene-styrene copolymers
- SB impact-resistant polystyrene
- antioxidants on the basis of their mechanism of action between primary and secondary antioxidants.
- the most important primary antioxidants are the so-called sterically hindered phenols, alongside secondary aromatic amines.
- the latter play only a subordinate role, especially in the case of thermoplastics, because of their product-discoloring tendency.
- Primary antioxidants act as radical scavengers, while the secondary ones (porphites, thioethers) decompose hydroperoxides. In practice, synergistic, ie complementary mixtures of primary and secondary anti-oxidants are often used.
- the sterically hindered phenols on the market have a large structural diversity: thiobisphenols, alkylidene bisphenols, alkylphenols, hydroxybenzyl compounds, acylaminophenols, hydroxyphenylpropionates (R. Gumbleter and H. Müller, Taschenbuch der Kunststoff-Additive, 2nd edition, 1983, pp. -9f., Carl Hanser Verlag Kunststoff).
- stabilizers that are harmless to health must be used, preferably those that also occur in natural foods.
- Vitamin E ( ⁇ -tocopherol), which belongs to the sterically hindered phenols, has already been described as an efficient stabilizer.
- EP 384 472 describes the use of vitamin E for packaging material made of polystyrene, in conjunction with light stabilizers.
- EP 408 693 describes stabilizer mixtures for styrene polymers made from vitamin E and mono / di / triglycerides.
- Cylinder and lamella morphology is found particularly in block copolymers, e.g. made of styrene and butadiene.
- block copolymers e.g. made of styrene and butadiene.
- the rubber phase is subjected to a considerably higher load during processing. As a result of the direct chemical linkage with the hard phase, tensions in the rubber phase are reduced less and the thermal-oxidative damage is greatly facilitated.
- block copolymers are easily accessible by anionic polymerization and have been known for a long time (see, for example, in M. Szwarc: “Carbanions, Living Polymers and Electron Transfer Processes, John Wiley Publ. 1968).
- block copolymers include the star-shaped branched styrene-butadiene block copolymers according to the invention with a predominant styrene content, as described, for example, in US Pat. No. 3,639,517 (70 to 95% styrene, 5 to 30% butadiene), DE-PS 25 50 227 and DE-OS 25 50 226 (60 to 95% styrene, 5 to 40% butadiene) can be described. It was found that in particular a mixture of the secondary antioxidant phosphite with vitamin E shows an excellent stabilizing effect in styrene / butadiene block copolymers.
- A is a block copolymer segment comprising at least one polystyrene block molecular weight to 230,000 [g / mol] and one polybutadiene block * er molecular weight from 2000 to 30,000 [g / mol] and B ei ⁇ nen block copolymer segment comprising at least a respective Polystyrol ⁇ the molar mass means 2000 to 60,000 [g / mol] and a polybutane block of the molar mass 2000 to 30,000 [g / mol], the total molar mass A: 50,000 to 250,000 [g / mol] and that of B: 5000 up to 75,000 tg / mol], the block transitions are sharp or smeared and the star load number m + n is a total of 3 to 15, with the proviso that m ⁇ n, and / or a linear styrene-butadiene block copolymer with at least 2 styrene blocks and
- an organic phosphite is additionally contained.
- this is tris (nonylphenyl phosphite), TNPP.
- Tocopherol is used in a concentration of 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight. It can be added to the polymers in any known or usual way, e.g. in pure form directly during processing, by premixing antioxidant and unstabilized polymer granules, by premixing antioxidant and polymer in solution and joint degassing or in the form of a concentrate (masterbatch).
- the organic phosphite is added in an amount of 0.1 to 2% by weight, preferably 0.2 to 1% by weight.
- R alkyl, aryl, cycloalkyl or combinations thereof.
- Examples are tris (nonylphenyl) phosphite, diphenyldecylphosphite, didecylphenylphosphite, phenyldi (2-ethylhexyl) phosphite, methyldiphenylphosphite, triphenylphosphite, tris (2, dimethylphenyl) phosphite, phenyldicyclohexylphosphylphosphite, trimethylphosphite, trimethyl - phenyl phosphite, di (2-ethylcyclohexyl) n-butyl phosphite, 3-cyclopentylpropyldihexyl phosphite.
- Tris (nonylphenyl) phosphite (TNPP) is preferably used.
- the organic phosphite is in turn stabilized with an amine compound, in particular triisopropanolamine in an amount of 0.1 to 5% by weight, based on 100% by weight of organic phosphite.
- an amine compound in particular triisopropanolamine in an amount of 0.1 to 5% by weight, based on 100% by weight of organic phosphite.
- Processing is understood to mean all customary methods with which thermoplastically processable polymers are melted and reshaped, e.g. via extruders, injection molding machines, kneaders, etc.
- the processing stability can be checked in the case of styrene-butadiene block copolymers with cylinder and lamella morphology, e.g. with the aid of the measuring device from Göttfert, Buchen known as Rheograph 2000.
- the polymer is pressed as a melt through a nozzle, similarly to extruder or injection molding processing.
- the extrusion pressure in the die is measured at constant melt temperature and constant shear rate.
- the crosslinking of the rubber phase begins due to the thermal-oxidative damage to the polymer. This increases the melt viscosity and thus the extrusion pressure.
- the effect of a stabilizer can be recognized by a more or less delayed increase in the extrusion pressure compared to the non-stabilized material.
- the extrusion pressure p is measured during the measuring time of 24 min.
- the pressure difference between the start and end of the measuring time, the so-called cross-linking pressure p v - is used as a measure of processing stability. 1 to 3. Examples and comparative experiment
- Example 1 a star-branched styrene-butadiene block copolymer was prepared.
- the viscosity number (VZ) was 83.5 ml / g.
- the polymer was not precipitated with methanol, but was first divided as a solution into 3 equal portions, taking care to strictly exclude air by blanketing with nitrogen.
- the 3 samples were stabilized according to the list below by adding antioxidants and then extruded and granulated by gentle degassing of the solvent in a Werner & Pfleiderer ZSK 25 twin-screw extruder at 200 ° C.
- 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate is available under the trade name ⁇ Irganox 3952.
- the samples of the examples were measured with a viscosity measuring device from Gottfert (Rheograph 2000) at a temperature of 290 ° C. and a shear rate of 1.44 ⁇ 10 1 s 1 .
Landscapes
- 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 une matière de moulage composée de polymères séquencés styrène-butadiène, obtenus par polymérisation anionique, de la formule générale (I) dans laquelle A désigne une section de polymère séquencé comprenant une séquence polystyrène dont le poids molaire est compris entre 3.000 et 230.000 [g/mole] et une séquence de polybutadiène dont le poids molaire est compris entre 2.000 et 30.000 [g/mole], B désigne une section de polymère séquencé comprenant au moins un séquence polystyrène dont le poids molaire est compris entre 2.000 et 60.000 [g/mole] et une séquence polybutadiène dont le poids molaire est compris entre 2.000 et 30.000 [g/mole]. Le poids molaire de A est compris entre 50.000 et 250.000 [g/mole] et celui de B est compris entre 5.000 et 75.000 [g/mole]. Les transitions entre séquences sont marquées ou maculées et le nombre de branches de l'étoile m+n est compris entre 3 et 15, sous réserve que m « n. Cette matière de moulage comprend également un copolymère séquencé styrène-butadiène linéaire comportant au moins 2 séquences polystyrène et au moins une séquence polybutadiène, auxquelles les données de poids molaire mentionnées ci-dessus sont applicables, et entre 0,01 % et 1 % en poids, par rapport au polymère, de α-tocophérol.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4420769A DE4420769A1 (de) | 1994-06-15 | 1994-06-15 | Mit alpha-Tocopherol stabilisierte Styrol/Butadien-Blockcopolymere |
DE4420769 | 1994-06-15 | ||
PCT/EP1995/002212 WO1995034600A1 (fr) | 1994-06-15 | 1995-06-08 | POLYMERES SEQUENCES STYRENE-BUTADIENE STABILISES PAR α-TOCOPHEROL |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0765362A1 true EP0765362A1 (fr) | 1997-04-02 |
Family
ID=6520560
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95923266A Ceased EP0765362A1 (fr) | 1994-06-15 | 1995-06-08 | POLYMERES SEQUENCES STYRENE-BUTADIENE STABILISES PAR $g(a)-TOCOPHEROL |
Country Status (5)
Country | Link |
---|---|
US (1) | US5877242A (fr) |
EP (1) | EP0765362A1 (fr) |
JP (1) | JPH10501834A (fr) |
DE (1) | DE4420769A1 (fr) |
WO (1) | WO1995034600A1 (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4443361A1 (de) * | 1994-12-06 | 1996-06-13 | Basf Ag | Mit alpha-Tocopherol, einem organischen Phosphit und einem sterisch gehinderten Phenol stabilisierte Styrol/Butadien-Blockcopolymere |
DE19521848A1 (de) * | 1995-06-16 | 1996-12-19 | Basf Ag | Stabilisierung von Polymerisaten des Styrols oder einer (Meth)acrylverbindung |
JP2001081250A (ja) * | 1999-07-14 | 2001-03-27 | Mitsui Chemicals Inc | ポリオレフィン樹脂組成物 |
JP2002194141A (ja) * | 2000-12-22 | 2002-07-10 | Sumitomo Chem Co Ltd | ブタジエン重合体成形品の製造法 |
BRPI0514737A (pt) * | 2004-08-30 | 2008-06-24 | Cargill Inc | composições de tocoferol e usos |
DE102004051924A1 (de) * | 2004-10-25 | 2006-04-27 | Basf Ag | Nanokomposit aus sternförmigen Styrol-Butadien-Blockcopolymeren und Schichtsilikaten |
NZ735860A (en) * | 2010-12-13 | 2019-05-31 | Cytec Tech Corp | Processing additives and uses of same in rotational molding |
US20130053486A1 (en) * | 2011-08-29 | 2013-02-28 | 3M Innovative Properties Company | Sealant materials and methods of using thereof |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3639517A (en) * | 1969-09-22 | 1972-02-01 | Phillips Petroleum Co | Resinous branched block copolymers |
DE2550227C2 (de) * | 1975-11-08 | 1984-12-20 | Basf Ag, 6700 Ludwigshafen | Verzweigte Blockcopolymerisate und Verfahren zu ihrer Herstellung |
DE2550226C2 (de) * | 1975-11-08 | 1984-12-13 | Basf Ag, 6700 Ludwigshafen | Verzweigte Blockcopolymerisate und Verfahren zu ihrer Herstellung |
JPS5474851A (en) * | 1977-11-28 | 1979-06-15 | Kureha Chem Ind Co Ltd | Vinyl chloride resin composition |
US4489099A (en) * | 1983-02-28 | 1984-12-18 | The Goodyear Tire & Rubber Company | Vitamin E/DLTDP stabilizer system for chewing gum SBR |
US4584346A (en) * | 1984-02-29 | 1986-04-22 | Phillips Petroleum Company | Craze-resistant transparent resinous polymodal block copolymers |
DE3634531A1 (de) * | 1986-10-10 | 1988-04-14 | Basf Ag | Stabilisatorgemische fuer kunststoffe |
JP2857882B2 (ja) * | 1988-11-02 | 1999-02-17 | 富山化学工業株式会社 | ピロキシカムのプラスター剤 |
DE58906177D1 (de) * | 1988-12-23 | 1993-12-16 | Basf Ag | Stabilisatorgemische für kunststoffe. |
EP0384472B1 (fr) * | 1989-02-23 | 1997-09-10 | Fuji Photo Film Co., Ltd. | Composition de résine et matériau d'emballage pour matériaux sensibles à la lumière |
US5384349A (en) * | 1993-12-06 | 1995-01-24 | Phillips Petroleum Company | Conjugated diene/monovinylarene copolymers and preparation thereof |
-
1994
- 1994-06-15 DE DE4420769A patent/DE4420769A1/de not_active Withdrawn
-
1995
- 1995-06-08 JP JP8501591A patent/JPH10501834A/ja active Pending
- 1995-06-08 US US08/750,670 patent/US5877242A/en not_active Expired - Fee Related
- 1995-06-08 WO PCT/EP1995/002212 patent/WO1995034600A1/fr not_active Application Discontinuation
- 1995-06-08 EP EP95923266A patent/EP0765362A1/fr not_active Ceased
Non-Patent Citations (1)
Title |
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See references of WO9534600A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE4420769A1 (de) | 1995-12-21 |
US5877242A (en) | 1999-03-02 |
WO1995034600A1 (fr) | 1995-12-21 |
JPH10501834A (ja) | 1998-02-17 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 19961204 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT NL |
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17Q | First examination report despatched |
Effective date: 19980401 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
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18R | Application refused |
Effective date: 19990225 |