WO1982002207A1 - Procede de preparation de pieces faconnees en poly-olefines - Google Patents

Procede de preparation de pieces faconnees en poly-olefines Download PDF

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Publication number
WO1982002207A1
WO1982002207A1 PCT/CH1981/000081 CH8100081W WO8202207A1 WO 1982002207 A1 WO1982002207 A1 WO 1982002207A1 CH 8100081 W CH8100081 W CH 8100081W WO 8202207 A1 WO8202207 A1 WO 8202207A1
Authority
WO
WIPO (PCT)
Prior art keywords
parts
polyolefin
phosphite
aqueous medium
per
Prior art date
Application number
PCT/CH1981/000081
Other languages
German (de)
English (en)
Inventor
Ag Georg Fischer
Original Assignee
Voegeli Marcel
Strehler Willi
Naberfeld Thomas
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 Voegeli Marcel, Strehler Willi, Naberfeld Thomas filed Critical Voegeli Marcel
Publication of WO1982002207A1 publication Critical patent/WO1982002207A1/fr

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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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • Polyolefin pipes carrying water or aqueous media show at elevated temperature and below. Compressive stress is not a reliable creep behavior. Depending on. Medium compositions have different test water qualities and / or a different test setup shows that pipes can surprisingly, chemically decompose from the inside out.
  • the amorphous part of the polyolefin structure is oxidatively degraded after an induction period.
  • the material only suffers pitting, which expands to make the material unsuitable.
  • Polyolefins are permeable to oxygen. If oxygen is used in a closed system made of polyolefinic material, the deficit of oxygen is compensated for by the wall and that by a progressively damaged polyolefinic partition.
  • transition metal ions of Cr 3+ , Mn 2+ , Fe 3+ , Co 2+ , Cu 2+ , 2n 2+ and oxo complexes of Ti and vanadium which are typically present in drinking water, process water and underfloor heating water applications can cause devastatingly rapid material degradation after an induction period.
  • a catalytically accelerated decomposition reaction dominates and determines the service life of the pipe or the shaped part depending on the temperature and pressure.
  • the desired decomposition not catalyzed by transition metal ions indicates a high voltage dependence
  • the catalyzed decomposition is indicated by a voltage dependence that is several times lower.
  • the present invention was based on the object of eliminating these disadvantages of the conventional polyolefin parts and improving the long-term durability of polyolefin parts at elevated temperature and / or pressure and contact with aqueous, aggressive media.
  • additives are fixed to the polymer matrix with a chemically compatible reactive resin and the melt stabilized in this way is processed into a molded part.
  • Polypropylene copolymers, polypropylene - (1) and crosslinked polyethylenes have proven to be particularly suitable polyolefins, but polybutene - (1) to a particularly large extent.
  • Copper (II) ion deactivators which have been selected from the group consisting of 1,2-dicarboxylic acid dihydrazides, 1,2-dicarboxylic acid dihydrazones, the substituted or unsubstituted benzoyl hydrazides and hydrazones or triazoles, preferably oxalyl bis (benzylidene hydrazide), oxalyl dihydrazide, m-nitrobenzide or 1,2,4-triazole is preferred.
  • the copper (II) ion deactivators are used in an amount of 0.1 to 0.8, preferably 0.1 to 0.6 parts, per 100 parts of polyolefin.
  • antioxidants are those having a 3,5-di-tert-butyl-4-hydroxy-phenyl group, for example tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinol namat)] - methane.
  • Bis [2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) terephthalate] and 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocinnamate are also suitable oxidation inhibitors .
  • the amounts used vary between 0.1 to 0.7 parts, preferably 0.4 parts, per 100 parts of polyolefin.
  • Dialkyl sulfides for example dilauryl thio-dipropionate, have proven to be particularly suitable as sulfidic synergists of the oxidation inhibitor.
  • the amounts used varied between 0.1 to 0.7 parts, preferably from 0.4 parts, to 100 parts of polyolefin.
  • a whole range of phosphoric acid esters for example the di-stearyl phosphite, the tri-stearyl phosphite, a pentaerythrityl phosphite (preferably - the acetoacetic acid dipentaerythritol phosphite ester or the isophthalic acid dipentaerythritol phosphite ester), a pentaerythrityl diphosphite phosphite (preferably) Sugar alcohol phosphite (preferably di-stearyl- ⁇ -hydroxytriacontyl-sorbityl triphosphite) or a triaryl phosphite) are suitable for the process according to the invention.
  • a pentaerythrityl phosphite preferably - the acetoacetic acid dipentaerythritol phosphite ester or the isophthalic acid dipentaerythritol phos
  • phosphorous acid esters which have an mp of 80-120 ° C., an optimum of 100 ° C.
  • an organic phosphonite can also be used.
  • the action of the sulfidic synergist is further enhanced by adding a wax with a molecular weight of 200-8000, preferably 400-4000, in an amount of 5-75 parts per 100 parts of phosphorous acid ester.
  • the total concentration of phosphorous acid ester is advantageously chosen between 0.01 to 0.15 parts, preferably 0.2 to 0.8 parts per 100 parts of polyolefin.
  • a whole series of dialkyl disulfides can be used for the process according to the invention, in particular that of the formula (S-CH 2 -CH 2 -COO-C 18 H 37 ) 2 in an amount of 0.1 to 0.7 parts, preferably 0.4 Parts, to 100 parts polyolefin.
  • a suitable, chemically compatible reactive resin preferably an epoxy resin, is added to the polyolefin melt.
  • Bisphenol- ⁇ -epichlorohydrine epoxy resins with an epoxy equivalent of 500-1000 are particularly suitable for this purpose, in an amount of 0.4 to 1.0 parts per 100 parts of polyolefin.
  • the effect of the reactive resin goes beyond the possible chemical reactions during melt molding with reactive groups from stabilizing additives and / or reactive groups, processing-related changes in the polymer and / or through associates and / or morphological influences.
  • the structure of the material side facing the aqueous medium can be compressed when the polyolefin melt is processed to form the molded part.
  • Another measure according to the invention is the selected stress state in the molded part.
  • the aim is to have a material interface that is prestressed under pressure and that faces the aqueous medium, and one that is prestressed under tension that faces the aqueous medium Interface facing away from the medium during melt molding. This requires modifications in the sense of reverse cooling.
  • the advantages achieved by the invention are essentially to be seen in the fact that a new synergistic additive selection and. a fixation of the additives used in the polyme matrix, which can additionally be structurally optimized on the surface in accordance with the type of use of the molded part, the transition metal ions Fe 3+ , Cu 2+ , Zn 2+ etc., as are present in aggressive aqueous media, are complexed into catalytically ineffective chelates by the additives incorporated into the polymer matrix, within amorphous areas, whereby the long-term durability behavior of the polyolefin forrest parts produced according to the invention is decisively improved.
  • This granulate was further processed, for example, into 16 ⁇ 2 mm tubes using an extruder.
  • the heat removal after melt molding was critical.
  • the interior of the tube was cooled with a water spray at the nozzle outlet for 0.5 to 0.8 seconds.
  • the heat of vaporization and evaporation of the sprayed water had 5 to 10 times the heat content compared to the melt deformed into the tube until it cooled below the solidification point of the tube.
  • the molded part (lg) produced according to the invention shows, compared to commercial polybutenes - (1) in 10 ml of an aqueous metal ion solution composed of 1g copper (II), 1g Zn (II) or 1g Fe (III) per liter of water in contact with the Oxygen from 50 ml air, at pH 1 after 1000 hours a greatly reduced oxygen consumption (suppression) of approx. 14%.
  • the creep behavior of 15 ⁇ 2 mm tubes, extruded from the material produced according to the invention, shows in transition metal ion-containing water, inside and outside with non-ferrous metal screw connections, an extended service life of 0.65 logarithmic units per unit of ring tension difference. tested between 18 and 19 bar.
  • Example 1 After a 10-fold dilution with polybutene- (1), the procedure was analogous to Example 1. Water in contact with extruded pipes made of the material produced according to the invention shows excellent smell and taste properties; these tubes show a significantly improved creep rupture behavior compared to conventional tubes.

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

Le procede de preparation de pieces faconnees en poly-olefines, selon l'invention, consiste en l'utilisation d'additifs de stabilisation appropries et compatibles, ainsi qu'en l'utilisation d'une resine reactive; cette derniere permettant de fixer les additifs utilises au polymere-porteur L'application pratique de telles pieces faconnees dans le domaine des installations sanitaires, du chauffage par le plancher, du transport et de l'entreposage de milieux liquides a temperature elevee et/ou sous pression demontre leur durabilite notablement amelioree.
PCT/CH1981/000081 1980-12-29 1981-07-15 Procede de preparation de pieces faconnees en poly-olefines WO1982002207A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
WOCH80/00163801229 1980-12-29
PCT/CH1980/000163 WO1982002206A1 (fr) 1980-12-29 1980-12-29 Procede de preparation de pieces faconnees en polyolefines

Publications (1)

Publication Number Publication Date
WO1982002207A1 true WO1982002207A1 (fr) 1982-07-08

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/CH1980/000163 WO1982002206A1 (fr) 1980-12-29 1980-12-29 Procede de preparation de pieces faconnees en polyolefines
PCT/CH1981/000081 WO1982002207A1 (fr) 1980-12-29 1981-07-15 Procede de preparation de pieces faconnees en poly-olefines

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/CH1980/000163 WO1982002206A1 (fr) 1980-12-29 1980-12-29 Procede de preparation de pieces faconnees en polyolefines

Country Status (2)

Country Link
EP (2) EP0067808A1 (fr)
WO (2) WO1982002206A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2252324A (en) * 1990-12-20 1992-08-05 Bp Chem Int Ltd Stabilizer composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03137146A (ja) * 1989-10-24 1991-06-11 Ube Ind Ltd ポリプロピレン系樹脂組成物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1234023B (de) * 1959-02-05 1967-02-09 Sun Oil Co Verfahren zum Stabilisieren von isotaktischem Polypropylen
DE2164234A1 (de) * 1970-12-30 1972-07-13 S.A. Argus Chemical N.V., Brüssel 3-Amido-l,2,4-triazole, Olefinpolymer-Stabilisatoren und diese enthaltende Olefinpolymerprodukte
BE854443A (fr) * 1977-05-10 1977-11-10 Argus Chem Coesters de phenols hydroxyliques
DE2748164A1 (de) * 1976-11-11 1978-05-24 Ingen Housz Jan Verfahren und vorrichtung zur herstellung eines aussenkalibrierten rohrs aus einem thermoplastischen kunststoff mittels extrusion
EP0019103A1 (fr) * 1979-04-26 1980-11-26 Hoechst Aktiengesellschaft Résines époxyde contenant des groupes phénoliques, leur utilisation et compositions de matières plastiques les contenant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1234023B (de) * 1959-02-05 1967-02-09 Sun Oil Co Verfahren zum Stabilisieren von isotaktischem Polypropylen
DE2164234A1 (de) * 1970-12-30 1972-07-13 S.A. Argus Chemical N.V., Brüssel 3-Amido-l,2,4-triazole, Olefinpolymer-Stabilisatoren und diese enthaltende Olefinpolymerprodukte
DE2748164A1 (de) * 1976-11-11 1978-05-24 Ingen Housz Jan Verfahren und vorrichtung zur herstellung eines aussenkalibrierten rohrs aus einem thermoplastischen kunststoff mittels extrusion
BE854443A (fr) * 1977-05-10 1977-11-10 Argus Chem Coesters de phenols hydroxyliques
EP0019103A1 (fr) * 1979-04-26 1980-11-26 Hoechst Aktiengesellschaft Résines époxyde contenant des groupes phénoliques, leur utilisation et compositions de matières plastiques les contenant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 85, No. 8, published on 23 august 1976, (columbus, Ohio, US), see page 37, left-hand column, Abstract 47 573j CS, A, 159524, LUSTON JOSEF u.a. 15-08-1975 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2252324A (en) * 1990-12-20 1992-08-05 Bp Chem Int Ltd Stabilizer composition

Also Published As

Publication number Publication date
EP0067817A1 (fr) 1982-12-29
WO1982002206A1 (fr) 1982-07-08
EP0067808A1 (fr) 1982-12-29

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