EP0566718A1 - Stabilisants pour matieres plastiques - Google Patents

Stabilisants pour matieres plastiques

Info

Publication number
EP0566718A1
EP0566718A1 EP19920922961 EP92922961A EP0566718A1 EP 0566718 A1 EP0566718 A1 EP 0566718A1 EP 19920922961 EP19920922961 EP 19920922961 EP 92922961 A EP92922961 A EP 92922961A EP 0566718 A1 EP0566718 A1 EP 0566718A1
Authority
EP
European Patent Office
Prior art keywords
stabilizing
component
weight
tocopherol
mixture
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
Application number
EP19920922961
Other languages
German (de)
English (en)
Inventor
Michael GMÜNDER
Terence John Henman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
F Hoffmann La Roche AG
Ciba Spezialitaetenchemie Holding AG
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 F Hoffmann La Roche AG, Ciba Spezialitaetenchemie Holding AG filed Critical F Hoffmann La Roche AG
Publication of EP0566718A1 publication Critical patent/EP0566718A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/527—Cyclic esters
    • 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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2

Definitions

  • This invention relates to stabilizers for plastic materials, and more specifically, to stabilizing mixtures for improving the colour and processing stability of plastic materials.
  • United States Patent No. 4,806,580 discloses stabilizer mixtures for stabilizing plastic material, e.g. polyethylene or polypropylene, in
  • the disclosed stabilizer mixtures contain (a) a chroman derivative, e.g. dl- ⁇ -tocopherol, and (b) an organic phosphite or phosphonite in a weight ratio (a:b) of 1:5 to 1:14.
  • a chroman derivative e.g. dl- ⁇ -tocopherol
  • an organic phosphite or phosphonite in a weight ratio (a:b) of 1:5 to 1:14.
  • Japanese Patent Publication (Kokai) No. 86036/1987 discloses stabilized polyolefin compositions, e.g. polypropylene, containing, per 100 parts by weight of the polyolefin, 0.005 to 0.5 parts by weight of a compound selected from the vitamin E group and 0.01 to 0.5 parts by weight of a bisaryl pentaerythrityl diphosphite(I) or a triaryl phosphite(II).
  • Japanese Patent Publication (Kokai) No. 55043/1979 discloses stabilized polyolefin compositions, e.g. polyethylene and polypropylene, containing a compound from the vitamin E group and various phosphites. In Examples 1-12 thereof the ratios of vitamin E:phosphite evaluated in polypropylene are 1:1.67 and 1:3.33.
  • the present invention provides stabilizing mixtures for plastic materials containing polypropylene comprising
  • R 1 signifies hydrogen or C 1-6 -alkyl
  • R 2 signifies halogen, C 1-18 -alkyl, C 1-18 -alkoxy or aryloxy
  • R 3 , R 4 , R 5 and R 6 each independently, signify isopropyl or straight- or
  • weight ratio of component (a) to component (b) is from about 1:0.5 to about 1:20.
  • tocopherol compound refers to a compound having the basic tocopherol structure of the vitamin E group.
  • Preferred tocopherol compounds for use as component (a) of the present stabilizing mixtures are ⁇ -tocopherol and ⁇ -tocopherol, particularly tile first-mentioned tocopherol compound.
  • other 6-chromanol compound indicates in particular substituted chroman-6-ols (in common with the aforementioned "tocopherol compounds) featuring the same substitution paterns on their benzene moiety as ⁇ -, ⁇ -, ⁇ - and ⁇ -tocopherols and, at the 2-position, two methyl groups or a methyl and a hydroxymethyl group.
  • chroman-6-ols are 2-hydroxymethyl-2,5,7,8-tetramethylchroman-6-ol and 2,2,5,7,8-pentamethylchroman-6-ol.
  • second antioxidant refers to those compounds which are hydroperoxide decomposers, i.e. which have the ability to react with hydroperoxides to yield non-radical products, essentially decomposing hydroperoxides into stable by-products.
  • Such compounds are the above-defined (phosphorus-containing) compounds of formula I.
  • any alkyl group (as such or as part of "alkoxy") which contains at least 3 carbon atoms may be straight- or branched-chain, unless otherwise specified.
  • aryloxy there is to be understood in particular phenoxy which is either unsubstituted or substituted with up to three C 1-4 -alkyl groups situated in the 2- and/or 4- and/or 6-position(s).
  • halogen embraces all four halogens, but preferably signifies fluorine. If R 1 signifies alkyl, this is preferably methyl.
  • the alkyl substituents signified by R 3 , R 4 , R 5 and R 6 are preferably identical, even more preferably all tert.butyl.
  • Particularly preferred compounds I for use as the component (b) of the present stabilizing mixtures are 2,2'-ethylidene-bis(4,6- di-tert.butylphenyl) fluorophosphonite (available from Ethyl Corporation, U.S.A., under the trade name Ethanox ® 398) and 2,2'-methylene-bis(4,6-di- tert.butylphenyl) octylphosphite (available from Argus Chemical Corp., Japan, under the trade name Mark HP-101.
  • the compounds of formula I are known or can be produced using methods known per se (see e.g. European Patent Publications 312790 and 357048).
  • plastic material containing polypropylene refers to those plastic materials which contain only polypropylene, i.e. homopolymers, copolymers which contain as one of the repeating units the polypropylene monomer moiety, or blends of polypropylene and one or more other polymers.
  • polypropylene i.e. homopolymers, copolymers which contain as one of the repeating units the polypropylene monomer moiety, or blends of polypropylene and one or more other polymers.
  • the stabilizing mixtures of the present invention there may be present not only one tocopherol or other 6-chromanol compound (a) and one phosphorus-containing secondary antioxidant of formula I (b) but also, as desired, one or more further compounds (a) and/or (b).
  • the definition of the inventive stabilizing mixtures is always to be so interpreted, and in those cases where more than one tocopherol or ot. 6-chromanol compound and/or more than one phosphorus-containin econdary antioxidant are present the weight ratio 1:0.5 to 1:20 refers to total component (a) and/or (b).
  • the weight ratio of component (a) to component (b) is preferably from 1:1 to 1:10, even more preferably from 1:1 to 1:5, and most preferably about 1:4.
  • a particularly preferred stabilizing mixture for plastic materials according to the present invention consists essentially of ⁇ -tocopherol as the component (a) and 2,2'-ethylidene-bis(4,6-di-tert.butylphenyl) fluorophosphonite as the component (b) in a weight ratio (a):(b) of about 1:4.
  • the stabilizing mixtures of the present invention may be produced by simple physical mixing of the components (a) and (b) with each other in the desired weight ratio. Preferably an intimate, homogeneous mixture of the two components is thereby achieved.
  • the methods of admixture and the equipment used for this purpose are well known to the person skilled in the art.
  • the physical mixing process represents a further aspect of the present invention.
  • the stabilizing mixtures of the present invention featuring the ratio of (a):(b) of from about 1:0.5 to about 1:20 by weight produce improved
  • the methods of incorporating the stabilizing mixtures of the present invention into the plastic materials to be stabilized thereby may be effected by the conventional methods which are generally utilized for the stabilization of plastic materials by additives. These methods are well known per se by persons skilled in the pertinent art and may involve the incorporation of the stabilizing mixture as such or of the components (a) and (b) individually, in the correct ratio, at any convenient stage of the manufacture or processing of the plastic material. In one embodiment, a small portion of the total stabilizing mixture is added immediately after the polymerization itself, just before the subsequent drying stage, and the rest is incorporated during the pelletizing stage.
  • the stabilizing mixture according to the present invention is generally incorporated in a concentration of from about 0.005 to about 1%, preferably from 0.02 to 0.125%, by weight, based on the total weight of the components (a) and (b) in relation to the weight of the plastic material to be stabilized.
  • the present invention comprises as a further aspect plastic materials containing polypropylene, and articles manufactured therefrom,
  • stabilizing mixtures for stabilizing plastic material containing polypropylene also represents a further aspect of the present invention.
  • stabilizing formulations comprise (a) ⁇ - tocopherol and (b) one or more polyhydroxy compounds, wherein the weight ratio of component (a) to component (b) is from about 1:0.5 to about 1:4.
  • These stabilizing formulations may be produced by simple physical mixing of the two components (a) and (b) with each other in the desired weight ratio, preferably in such a way as to achieve an intimate,
  • the stabilizing formulations are clear solutions, which remain so even after being frozen and then thawed. The intimate mixing of the components is then suitably carried out by stirring together in suitable equipment, until a clear solution results.
  • the stabilizing formulations are particularly effective in stabilizing the plastic material in which they are incorporated against undesired discolouration, especially yellowing, during processing.
  • polyhydroxy compound embraces any compound featuring at least two hydroxyl groups.
  • Preferred such compounds are ethylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, triisopropanolamine, panthenol, boric acid, glyceryl monostearate and glyceryl(mono)caprylate/caprate.
  • plastic material embraces not only the “plastic materials containing polypropylene” as described hereinabove but also plastic materials,
  • thermoplastic materials which include other types of polymers, such as polyethylene, polyvinyl chloride, polystyrenes and polyurethanes. Accordingly, these plastic materials are not limited to those containing polypropylene, or even to polyolefines. Blends of two or more different types of polymers or copolymers are naturally included in the "plastic materials" to be stabilized by the present stabilizing formulations.
  • the plastic materials stabilized by the stabilizing formulations of the present invention are plastic materials containing polypropylene.
  • these stabilizing formulations feature a weight ratio of component (a) to component (b) of from 1:1 to 1:2, even more preferably of about 1:2.
  • the stabilizing formulations may contain, in addition to the aforementioned components (a) and (b), other additives to facilitate their preparation by mixing, e.g. emulsifying agents.
  • emulsifying agents for this purpose is glyceryl(mono)caprylate/caprate, available from Drew Chemical Co. under the trade name Drewmulse ® GMC-8. This may be used as the sole emulsifying agent or, if desired, in combination with one or more other suitable ingredients in an emulsifying system.
  • a particularly preferred emulsifying system consists of
  • glyceryl(mono)caprylate/caprate in combination with polyethylene glycol.
  • a particular class of the above stabilizing formulations consists of those comprising (a) ⁇ -tocopherol and (b) one or more polyhydroxy compounds, wherein the weight ratio of component (a) to component (b) is from about 1:0.5 to about 1:4, with the exclusion of a stabilizing formulation comprising
  • the present invention embraces the above-indicated process for producing these formulations, comprising, more particularly, mixing in the desired weight ratio the above-defined components (a) and (b) with each other, in appropriate cases until a clear solution is formed. If any other components, e.g. an emulsifying agent such as the aforementioned glycerol monocaprylate caprate, are to be present in the finished formulation these can be mixed with the components (a) and (b) simultaneously. Specific methods and equipment for the mixing process are well known to the person skilled in the art.
  • the present stabilizing formulations also improve the processing stability and colour stability, while maintaining the heat aging stability, of the plastic materials in which they are incorporated, particularly the colour stability.
  • the methods of incorporating these stabilizing formulations into the plastic materials to be stabilized thereby may in this case too be effected by conventional methods which are generally utilized for the stabilization of plastic materials by additives and which are well known by persons skilled in the pertinent art.
  • the stabilizing formulation is generally incorporated in a concentration of from about 0.01 to about 1% by weight, based on the total weight of the components (a) and (b) in relation to the weight of the plastic material to be stabilized, preferably in a concentration of 0.05 to 0.25% by weight. It has been found that these stabilizing formulations are readily incorporated at low concentrations and become well dispersed in the plastic material in which they are incorporated.
  • the present invention comprises as further aspects plastic materials, and articles manufactured therefrom, characterized in that they have been stabilized by incorporation therein of a stabilizing formulation according to the present invention and as defined hereinbefore, and the use of these stabilizing formulations for stabilizing such plastic materials.
  • the present invention comprises as a further aspect a stabilizing three-component mixture for plastic materials containing polypropylene comprising
  • polyhydroxy compound is to be interpreted in accordance with the previous definition pertaining to the stabilizing formulations of the. present invention. Furthermore, there may be present not only one phosphorus-containing secondary antioxidant of formula I (b) and one polyhydroxy compound (c) but also, as desired, one or more further compounds (b) and/or (c).
  • the definition of the inventive stabilizing three-component mixtures is always to be so interpreted, and in those cases where more than one phosphorus-containing secondary anti- oxidant of formula I and/or polyhydroxy compound are present the given percentage weight ranges for components (b) and (c) refer to total component (b) and/or (c).
  • the term "plastic material containing polypropylene” is to be interpreted as indicated hereinabove for the stabilizing mixtures of the present invention which comprise a tocopherol or other 6-chromanol compound and a phosphorus-containing secondary antioxidant of formula I.
  • the present stabilizing three- component mixtures also improve the processing stability, colour stability and heat aging stability of the plastic materials in which they are
  • stabilizing formulation is generally incorporated in a concentration of from about 0.01 to about 0.25% by weight, based on the weight of the plastic material to be stabilized.
  • the incorporation may also involve adding
  • the present invention comprises as further aspects plastic materials containing polypropylene, and articles manufactured therefrom,
  • the present invention also provides the above-defined stabilized plastic materials containing polypropylene, and articles manufactured therefrom, whenever subjected to ⁇ -irradiation at a dose of from about 0.5 to about 5.0 Mrad (such as is effected utilizing cobalt-60 as the source of ⁇ -irradiation).
  • Example 1 illustrates the present invention in its various aspects.
  • Unstabilized polypropylene homopolymers as powders (the “base powders"), were obtained from ICI (Chemicals and Polymers), Wilton, UK and are identified below as ICI-B, ICI-H and ICI-K. They were stored at low ambient temperature in a dark, unheated room.
  • Catalyst residues in these base powders were measured by plasma emission spectroscopy (Ti, Al) and a bomb method (CD, the approximate values found being: titanium, 25 ppm; aluminium, 30 ppm; and chlorine, 25 ppm.
  • the melt flow index (MFI) of the base powders were measured at
  • Stabilizers in powder form and masterbatches were blended into the appropriate amount of ICI-B, ICI-H or ICI-K powder using a Pascail Lab- Mixer II mixer, at about 23 rpm with a cycle time of about 5 minutes.
  • Melts were extruded through a 6 mm rod die, the lace fed into a water bath, through a haul off and air knife (to remove surface water) and granulated either in-line or collected and separately granulated later.
  • Extrusion was effected on a twin screw Brabender machine with counter-rotating screws, 30 mm diameter barrel and a L/D (length/diameter) ratio of 16:1. This extrusion was primarily for obtaining efficient blending of the additives with relatively little mechanicalwork being done on the polymer.
  • the approximate running conditions were as follows: - - - - - - - - - - - - - - - - - - - - - - - - - - - - Temperatures (°C)- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
  • Hopper zone 2 zone 3 die melt (rpm) (kg/h)
  • melt temperature chosen was substantially higher, being approximately 270°C, in order to show more clearly the different
  • Hopper zone 2 zone 3 die melt (rpm) (kg/h)
  • the first single screw pass (second overall pass) was granulated, the product (less 200 g as previously discussed) refed into the hopper and this procedure repeated twice more to obtain a sample that had been extruded a total of four times.
  • the colour values were measured on granules in enclosed cells on Minolta or Dr. Lange intruments using illuminant C or illuminant D65, respectively.
  • the machine outputs respectively Yxy and CIE (Commission Internationale de L'Eclairage) L*a*b*, were averages and the means converted to ASTM D1925 yellowness index (YI) values.
  • MFI was measured at 230°C/2.16 kg (BS 2782 Part 7 method 720A, equivalent to ASTM D1238 condition L). The lowest granule MFI was also remeasured at 190°C/10 kg, from which estimates of powder MFI at
  • Compression moulded plaques were obtained at 190°C; 30 g/170 g samples were used to press nominally 0.5 mm/3.0 mm thick mouldings respectively. In each case, a strip 1 cm wide was removed from the outside to avoid any contamination. Oven aging was determined on 5 cm square sections.
  • Oven aging was carried out in Gallenkamp OV330 size 2 circulating air ovens where temperature control was accurate to +/-1°C. Measurements were carried out at 150°C, 135°C and 120°C on duplicate samples arranged horizontally on stainless steel mesh trays. Initial signs of powdering were recorded, but in each case the embrittlement point was taken when a sample flexed manually through 180°C became brittle. Results were recorded using hour meters, with the average time in days for two samples taken as the embrittlement time.
  • Example 1 The procedure described in Example 1 was in principle repeated, but with a few differences as indicated hereinafter. Before the melt flow index, yellowness index and oven aging determinations were effected, part of the polypropylene having incorporated therein the stabilizing mixtures was subjected to ⁇ -irradiation, as also described in more detail hereinafter.
  • Starting polypropylene A ethylene-propylene copolymer, obtained from Rexene Inc., U.S.A. and of a type usually employed in ⁇ -irradiation
  • Extrusion The twin screw extruder and running conditions were as described previously, with the difference that only one extrusion pass was effected; 0.7 kg; screw speed 15 rpm; output approx. 7.5 kg/h; temperatures: hopper 220°C, zone 1 225°C, zone 2 230°C, zone 3 235°C, melt 230°C.
  • Lace was collected and granulated, and the initial melt flow index and yellowness index were determined as described in Example 1, using the same equipment. After compression moulding as before oven lives (days to embrittlement) were determined using circulating-air ovens at 70°C.
  • Irradiation A custom irradiation facility was used, with cobalt-60 as the source of ⁇ -irradiation.
  • the total irradiation dose was 2.5 Mrad, the mean dose rate 2.6 Mrad/h.
  • One set of granule samples was maintained at room temperature, and melt flow index and yellowness index were
  • E 398 Ethanox ® 398, 2,2'-ethylidene-bis(4,6-di-tert.butylphenyl) fluorophosphonite 3)
  • TNPP tris(p-nonylphenyl)phosphite
  • HP-10 Mark HP-10, 2,2'-methylene-bis(4,6-di-tert.butylphenyl) octylphosphite
  • GMC-8 Drewmulse ® GMC-8, glyceryl(mono)caprylate/caprate
  • MD 1024 Irganox ® MD 1024, N,N'-bis[ ⁇ -(3,5-di-tert.butyl-4-hydroxyphenyl)-propionyl]-hydrazide
  • XL-1 Naugard ® XL-1, 2,2'-oxamido-bis[ ⁇ - ⁇ 3-( ⁇ -[3,5-di-tert.butyl- 4-hydroxyphenyl]-propionyloxy) ⁇ -ethyl]
  • PEG-300 polyethylene glycol

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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

Mélanges stabilisants pour matières plastiques contenant du polypropylène. Ils comportent (a) un tocophérol ou un autre composé de 6-chromanol, et (b) un antioxydant secondaire contenant du phosphore, répondant à la formule (I) et caractérisé par le 2,2'-éthylidène-bis(4,6-di-tert.butylphényl) fluorophosphite et le 2,2'-méthylène-bis(4,6-di-tert.butylphényl) octylphosphite où le rapport de poids (a):(b) est compris entre 1:05 et 1:20 environ. Des formulations stabilisantes apparentées de près et destinées aux matières plastiques comportent (a) un alpha-tocophérol et (b) un ou plusieurs composés polyhydroxy où le rapport de poids (a):(b) est compris entre 1:05 et 1:4 environ. Des mélanges à trois composants destinés aux matières plastiques contenant du polypropylène comportent (a) de 4 à 50 % en poids environ de alpha-tocophérol, (b) de 4 à 70 % en poids environ d'un antioxydant secondaire contenant du phosphore et répondant à ladite formule (I), et (c) de 4 à 70 % en poids environ d'un composé polyhydroxy, le pourcentage global en poids des trois constituants (a), (b) et (c) s'élevant à 100. On peut produire ces mélanges et formulations stabilisant(e)s en mélangeant les constituants appropriés selon les rapports de poids appropriés. On a également prévu des matières plastiques ou des articles en matière plastique incorporant le mélange ou la formulation stabilisant(e), ainsi que l'utilisation de ces mélanges et formulations stabilisant(e)s dans la stabilisation des matières plastiques. En outre, on a prévu les matières plastiques ainsi stabilisées et contenant du polypropylène, ainsi que des articles constitués de ces matières plastiques et soumis à une irradiation gamma à une dose comprise entre 0,5 et 5,0 Mrad.
EP19920922961 1991-11-12 1992-11-09 Stabilisants pour matieres plastiques Ceased EP0566718A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9123976 1991-11-12
GB919123976A GB9123976D0 (en) 1991-11-12 1991-11-12 Stabilizers for thermoplastic materials

Publications (1)

Publication Number Publication Date
EP0566718A1 true EP0566718A1 (fr) 1993-10-27

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ID=10704465

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920922961 Ceased EP0566718A1 (fr) 1991-11-12 1992-11-09 Stabilisants pour matieres plastiques

Country Status (4)

Country Link
EP (1) EP0566718A1 (fr)
JP (1) JPH06504577A (fr)
GB (1) GB9123976D0 (fr)
WO (1) WO1993010175A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5308549A (en) * 1991-11-12 1994-05-03 Hoffmann-La Roche Inc. Stabilizers for thermo plastic materials
US5663223A (en) * 1994-08-11 1997-09-02 Zapata Technologies, Inc. Flavor protectant closure liner compositions
US5670255A (en) * 1995-01-23 1997-09-23 Ppg Industries, Inc. Antioxidant compositions for coating substrates, substrates coated with the same and methods for inhibiting the oxidation of such compositions applied to a substrate
US5594055A (en) * 1995-02-22 1997-01-14 Hoffmann-La Roche Inc. Antioxidant system for polyolefins
FI991634A (fi) * 1999-07-21 2001-01-22 Valtion Teknillinen Komonomeeri ja sillä polymerointivaiheessa stabiloitu polymeeri
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
CN117957279A (zh) 2021-09-09 2024-04-30 Sabic环球技术有限责任公司 具有改进的辐射稳定性的聚丙烯组合物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9310175A1 *

Also Published As

Publication number Publication date
WO1993010175A1 (fr) 1993-05-27
JPH06504577A (ja) 1994-05-26
GB9123976D0 (en) 1992-01-02

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