WO1993010175A1 - Stabilizers for plastic materials - Google Patents
Stabilizers for plastic materials Download PDFInfo
- Publication number
- WO1993010175A1 WO1993010175A1 PCT/EP1992/002572 EP9202572W WO9310175A1 WO 1993010175 A1 WO1993010175 A1 WO 1993010175A1 EP 9202572 W EP9202572 W EP 9202572W WO 9310175 A1 WO9310175 A1 WO 9310175A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- stabilizing
- component
- weight
- tocopherol
- plastic materials
- Prior art date
Links
- 0 *C1c2cc(*)cc(*)c2OP(*)Oc2c1cc(*)cc2* Chemical compound *C1c2cc(*)cc(*)c2OP(*)Oc2c1cc(*)cc2* 0.000 description 1
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
- United States Patent No. 4,806,580 discloses stabilizer mixtures for stabilizing plastic material, e.g. polyethylene or polypropylene, in
- the present invention provides stabilizing mixtures for plastic materials containing polypropylene comprising
- R 2 signifies halogen, C 1-18 -alkyl, C 1-18 -alkoxy or aryloxy
- weight ratio of component (a) to component (b) is from about 1:0.5 to about 1:20.
- 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.
- 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 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 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).
- 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.
- 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
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
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5508944A JPH06504577A (en) | 1991-11-12 | 1992-11-09 | Stabilizer for plastic materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9123976.4 | 1991-11-12 | ||
GB919123976A GB9123976D0 (en) | 1991-11-12 | 1991-11-12 | Stabilizers for thermoplastic materials |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993010175A1 true WO1993010175A1 (en) | 1993-05-27 |
Family
ID=10704465
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1992/002572 WO1993010175A1 (en) | 1991-11-12 | 1992-11-09 | Stabilizers for plastic materials |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0566718A1 (en) |
JP (1) | JPH06504577A (en) |
GB (1) | GB9123976D0 (en) |
WO (1) | WO1993010175A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0730001A1 (en) * | 1995-02-22 | 1996-09-04 | F. Hoffmann-La Roche Ag | Stabilizers for plastic materials |
EP0781107A1 (en) * | 1994-08-11 | 1997-07-02 | 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 |
WO2001005781A1 (en) * | 1999-07-21 | 2001-01-25 | Valtion Teknillinen Tutkimuskeskus | A comonomer, and a polymer stabilized with it during polymerization |
WO2023036705A1 (en) | 2021-09-09 | 2023-03-16 | Sabic Global Technologies B.V. | Polypropylene composition having improved radiation stability |
Families Citing this family (2)
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 |
JP2002194141A (en) * | 2000-12-22 | 2002-07-10 | Sumitomo Chem Co Ltd | Method of manufacturing butadiene polymer molded article |
-
1991
- 1991-11-12 GB GB919123976A patent/GB9123976D0/en active Pending
-
1992
- 1992-11-09 WO PCT/EP1992/002572 patent/WO1993010175A1/en not_active Application Discontinuation
- 1992-11-09 EP EP19920922961 patent/EP0566718A1/en not_active Ceased
- 1992-11-09 JP JP5508944A patent/JPH06504577A/en active Pending
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1, no. 91 (C-77)24 August 1977 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0781107A1 (en) * | 1994-08-11 | 1997-07-02 | Zapata Technologies, Inc. | Flavor protectant closure liner compositions |
EP0781107A4 (en) * | 1994-08-11 | 2001-03-07 | 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 |
US5747162A (en) * | 1995-01-23 | 1998-05-05 | Ppg Industries, Inc. | Substrates coated with antioxidant compositions and method for inhibiting the oxidation of such compositions applied to a substrate |
EP0730001A1 (en) * | 1995-02-22 | 1996-09-04 | F. Hoffmann-La Roche Ag | Stabilizers for plastic materials |
US5594055A (en) * | 1995-02-22 | 1997-01-14 | Hoffmann-La Roche Inc. | Antioxidant system for polyolefins |
WO2001005781A1 (en) * | 1999-07-21 | 2001-01-25 | Valtion Teknillinen Tutkimuskeskus | A comonomer, and a polymer stabilized with it during polymerization |
WO2023036705A1 (en) | 2021-09-09 | 2023-03-16 | Sabic Global Technologies B.V. | Polypropylene composition having improved radiation stability |
Also Published As
Publication number | Publication date |
---|---|
EP0566718A1 (en) | 1993-10-27 |
GB9123976D0 (en) | 1992-01-02 |
JPH06504577A (en) | 1994-05-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0542108B1 (en) | Stabilizers for plastic materials | |
US4806580A (en) | Stabilizer mixtures for plastics | |
EP2970633B1 (en) | Stabilized polymer compositions and methods of making same | |
DE69704864T2 (en) | STABILIZER COMPOSITIONS | |
JPH07119318B2 (en) | Stabilizer composition | |
WO1993010175A1 (en) | Stabilizers for plastic materials | |
EP1373392B1 (en) | Color improving stabilizing compositions comprising leucine | |
JPS62109840A (en) | Polypropylene composition | |
EP0714938A2 (en) | Polyketone stabilization | |
US3103501A (en) | - olefins containing alkylidene- | |
US3988293A (en) | Stabilizer system for polyolefins | |
US3859236A (en) | Stabilized vinyl halide polymer compositions | |
CN112538209B (en) | High-temperature-aging-resistant polypropylene composition | |
EP1854840B1 (en) | Master batch for resins | |
EP0237135B1 (en) | Thermally stable diphosphonate-type flame retardant additive for plastics | |
US4243581A (en) | Stabilized polypropylene composition | |
JP2002194230A (en) | Resin composition | |
US3636031A (en) | Antioxidant system for polyolefins | |
JPH0341135A (en) | Food container | |
EP3510094A1 (en) | Flame-retarded transparent polycarbonate compositions | |
EP0300542A1 (en) | Thermally stable diphosphonate-type flame retardant additive for plastics | |
WO2000005304A1 (en) | Method for reducing odor during processing of flame retardant polymers | |
EP0426912B1 (en) | Antioxidant polyolefin compositions | |
JPH01261443A (en) | Polypropylene composition | |
JPH03258892A (en) | Activating agent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): JP US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL SE |
|
ENP | Entry into the national phase |
Ref country code: US Ref document number: 1993 70428 Date of ref document: 19930608 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1992922961 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1992922961 Country of ref document: EP |
|
WWR | Wipo information: refused in national office |
Ref document number: 1992922961 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1992922961 Country of ref document: EP |