WO1999019397A1 - Polyolefine stabilisee - Google Patents

Polyolefine stabilisee Download PDF

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Publication number
WO1999019397A1
WO1999019397A1 PCT/NL1998/000572 NL9800572W WO9919397A1 WO 1999019397 A1 WO1999019397 A1 WO 1999019397A1 NL 9800572 W NL9800572 W NL 9800572W WO 9919397 A1 WO9919397 A1 WO 9919397A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
metal deactivator
polyolefin composition
stabilized
composition according
Prior art date
Application number
PCT/NL1998/000572
Other languages
English (en)
Inventor
Dieter Bilda
Reinhart Hammel
Wolfgang Warschewski
Original Assignee
Dsm N.V.
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 Dsm N.V. filed Critical Dsm N.V.
Priority to AU95603/98A priority Critical patent/AU9560398A/en
Publication of WO1999019397A1 publication Critical patent/WO1999019397A1/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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides

Definitions

  • the invention relates to a stabilized polyolefin composition which is characterized by a reduced rate of oxidative degradation in contact with metals and metal ions.
  • polyolefins in long-life applications, for instance in the area of building construction, has become increasingly important in recent years.
  • polyolefins are in practice exposed to oxidative attack from radicals (e.g. oxygen, UV irradiation), resulting in molecular weight reduction and finally in failure of the components made of the polyolefins .
  • This process can be inhibited by appropriate stabilization of the polyolefins, due to which a service life of more than 20 years can readily be ensured for polyolefin components, as a regular state-of-the-art achievement.
  • Catalytic acceleration of the oxidative degradation of polyolefins by metal or metal ions is particularly detrimental when these plastics are used in pressurized or heated water applications, for instance for drinking-water or sanitary installations, especially because in this application area an anticipated service life of more than 50 years is required in some cases .
  • the presence of metals or metal ions can never be fully excluded, as even in installations made entirely of plastics it is necessary to use metals for the supply lines, fittings, mountings, heating hoses, etc.
  • Oxidative degradation of the polyolefin occurs in particular where it enters into contact with copper or copper-containing alloys, such as brass. But other metals are also known to be responsible for catalytic acceleration of the oxidative degradation of polyolefins.
  • Oxidative degradation of polyolefins results in deterioration of the mechanical properties and premature degradation of the material.
  • oxidative degradation is reflected for instance in premature failure of the pipes. That is why it is important for these pipes to be stabilized against metals and metal ions that may be present in the system.
  • JP 01 188 543 A2 describes a polypropylene composition which besides polypropylene, antioxidants and an epoxide compound contains 0.01 to 5 wt . % of a metal deactivator.
  • the metal deactivator used is 2,2'- oxamido-bis- [ethyl-3 (3,5, -di-tert .butyl-4- hydroxyphenyDpropionate] .
  • This substance is available as Naugard XL-1 ® (Uniroyal Inc., USA).
  • the thermoplastic composition further contains filling agents. It makes the polymer more resistant against ageing under the influence of heat and metals .
  • JP 48 022 134 A also discloses a thermally stable polypropylene composition for use as cable sheathing.
  • This composition comprises a phenol- containing stabilization agent, as well as an inhibitor against copper-catalyzed degradation.
  • the inhibitor is a hydrazine derivative.
  • the composition in question shows improved stability properties in contact with copper plates and at high temperatures .
  • EP 048 562 Al discloses a stabilizing composition for polymers, in particular for thermal stabilization, which besides a phosphite compound comprises a phenol-containing oxamide.
  • the oxamide used is for instance a 2 , 2 ' -oxamido-bis- [ethyl- 3 (3, 5, -di-tert .butyl-4-hydroxyphenyl)propionate] .
  • a drawback of the stabilization systems according to the state of the art is that the metal deactivators which are used for stabilization of the polymer migrate out of the polymeric material. That is why stabilization by means of the state-of-the-art stabilization systems is unsatisfactory.
  • the technical objective of the invention therefore is to provide a novel stabilized polyolefin composition in which the migration of metal deactivators is suppressed and as a result of this a lasting stabilization of the polymers against metals and metal ions is achieved.
  • R 1 is a C_ to C 8 alkyl group
  • R 2 is hydrogen or a C x to C 8 alkyl group
  • X is a C_ to C 12 alkylene group
  • metal deactivator B being a phenol-containing hydrazide of formula II
  • R 1 and R 2 have the same meaning as in formula I and R 3 , R 4 are hydrogen or a C_ to C 8 alkyl group.
  • the stabilized polyolefin according to the invention is suitable in particular for the manufacture of moulded articles for various applications. Particularly preferred applications are pipes for heating and sanitary installations, sewage pipes, cooling water compensator reservoirs and brake fluid reservoirs.
  • the added amount of metal deactivator is preferably between 0.05 and 0.5 wt.%.
  • the added amount of metal desulphide is preferably between 0.2 and 0.7 wt.%.
  • the metal deactivators used preferably are benzene propionic acid, 3 , 5-bis (1, 1-dimethylethyl) -4- hydroxy,2- [3- [3, 5-bis (1, 1-dimethylethyl) -4- hydroxyphenyl] -1-oxo-propyl] hydrazide and/or 2,2'- oxamido-bis- [ethyl-3- (3,5, -di-tert .butyl-4- hydroxyphenyDpropionate] .
  • Zinc sulphide in particular is used as co-stabilizing metal sulphide.
  • polyolefins preferably chosen from the group comprising polypropylene, polyethylene, polybutene-1, polyisobutylene or mixtures of these.
  • Polypropylene is preferred in particular.
  • the stabilized polyolefin compositions are prepared by mixing the components, viz. the polyolefin, the metal deactivator and the metal sulphide. Subsequently, the mixture is melted, and extruded and granulated on a laboratory extruder. The granulate can be processed to the desired moulded articles.
  • the polyolefin compositions can also contain the customary auxiliary agents and stabilizers, such as for instance processing stabilizers, antioxidants, UV stabilizers, acid acceptors and filling agents.
  • auxiliary agents and stabilizers such as for instance processing stabilizers, antioxidants, UV stabilizers, acid acceptors and filling agents.
  • a further object of the invention relates to processing of the stabilized polyolefin composition to moulded articles which are stabilized against oxidative degradation due to metals and/or metal ions. It is particularly preferred for these moulded articles to be pipes for heating and sanitary installations, sewage pipes, cooling water compensator reservoirs and brake fluid reservoirs. In principle, the invention is suitable for all applications involving conveyance or storage of metal ions or metal -containing liquids.
  • the melt index was measured in g per 10 minutes in accordance with DIN/ISO 1133. Degradation test
  • the MFR 270°C/2.16 kg was determined in accordance with DIN/ISO 1133, in g per 10 minutes (measurement 1) .
  • the melt strand from measurement 1 was cut up and introduced into the MFR apparatus again (measurement 2) .
  • Measurement 3 was effected with the melt strand from measurement 2.
  • the test was carried out with extruded pipes, measuring 20 x 3.2 mm, in accordance with the 'KTW' [plastics and drinking water] recommendation of the working group for 'Drinking Water Interests' of the Plastics Committee of the German Public Health Board (Bundesgesundheidsblatt 22, 213, 1979) .
  • the pipes are rinsed with test water from original containers (e.g. mineral water out of glass bottles) and are then filled with the test water and stored for 6 hours at 60°C or for 9 days at room temperature. After cooling of the pipes and decanting into test cups of glass, the odour and taste are judged by at least three testers by comparison with water from the original containers . The testers do not know which water is in which test cup. The test result 'n.d.' means that none of the testers has found a difference in odour and taste .
  • Sets of three pipes 20 x 3.2 mm, length 370 mm, are provided with brass caps (Isiflo) and placed in a pipe testing device.
  • the following test conditions apply to all examples and comparative examples : the pipes are filled with water and are immersed in a water bath. The temperature of the water is 95°C, the peripheral stress, sigma, is 3.6 Mpa. Failure of a pipe results in a pressure drop in the test device.
  • the endurance times given in tables 1 and 2 are averages for sets of three identical pipes.
  • the pipes are manufactured on a single-screw extruder, type Reifenhauser S 60/25 d.
  • the temperature of the compound is 218°C and the output amounts to 27 kg/h.
  • the tool data are as follows: shell 24.0 mm, mandrel 18.4 mm, slit width 4.6 mm, calibration 20.9 mm.
  • concentration of the various additives a) , b) , c) and e) separately, as well as their combined concentration should be in accordance with the BGA and FDA guidelines for the use of plastics in food-contact applications.
  • Tne mixture is granulated by means of a laboratory extruder, type W&P P ZSK 30.
  • the granulate is processed to pipes of 20 x 3.2 mm.
  • the granulates and the pipes are subjected to tests.
  • the test results are presented in table 1.
  • Example I I I
  • the polypropylene moulding compound is prepared as in Example 1, except that the concentration of the additive component e) (metal deactivator Irganox MD 1024®) amounts to 0.2 wt.%.
  • concentration of the additive component e) metal deactivator Irganox MD 1024®
  • results of the tests are presented in table 1.
  • the results of the tests are presented in table 2.
  • the polypropylene moulding compound is prepared as in Example 3, except that 0.2 wt.% of 2,2'- oxamido-bis- [ethyl-3- (3,5, -di-tert .butyl-4- hydroxyphenyDpropionate] (tradename: Naugard XL-1®, from Uniroyal) is used as metal deactivator.
  • the results of the tests are presented in table 2.
  • The- results of the tests are presented in table 1. Comparative example 2
  • the pigmentation is of the same type as applied in Examples 3 and 4. The results of the tests are presented in table 2.
  • test results presented in table 1 are the same for all examples and comparative examples within the measurement accuracy, which means that important service properties of the pipes, such as organoleptic characteristics and service life, are not affected by the presence of Irganox MD 1024® metal deactivator.
  • the pipe endurance test is carried out with pipes with brass caps, the test conditions (high temperature, high peripheral stress sigma) are such that only ductile and brittle cracks occur and that material damage as a result of oxidation does not yet play a role. That is why no service life increase due to the presence of the metal deactivator is found. This will only become apparent with very long service times, as can be expected at low temperatures and low peripheral stress levels, in contrast to the test conditions.

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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

Cette invention concerne une composition de polyoléfine stabilisée qui contient un sulfure d'un métal ainsi qu'un désactiveur de métal A ou B ou un mélange de ces désactiveurs de métal. Le désactiveur de métal A consiste en un oxamide contenant du phénol et correspondant à la formule (I) où R1 représente un groupe alkyle C¿1? à C8, R?2¿ représente hydrogène ou un groupe alkyle C¿1? à C8, tandis que X représente un groupe alcylène C1 à C12. Le désactiveur de métal B consiste en un hydrazide contenant du phénol et correspondant à la formule (II) où R?1 et R2¿ sont tels que définis dans la formule (I), tandis R3 et R4 représentent hydrogène ou un groupe alkyle C¿1? à C8.
PCT/NL1998/000572 1997-10-11 1998-10-02 Polyolefine stabilisee WO1999019397A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU95603/98A AU9560398A (en) 1997-10-11 1998-10-02 Stabilized polyolefin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19745064 1997-10-11
DE19745064.4 1997-10-11

Publications (1)

Publication Number Publication Date
WO1999019397A1 true WO1999019397A1 (fr) 1999-04-22

Family

ID=7845320

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1998/000572 WO1999019397A1 (fr) 1997-10-11 1998-10-02 Polyolefine stabilisee

Country Status (2)

Country Link
AU (1) AU9560398A (fr)
WO (1) WO1999019397A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11365307B2 (en) * 2017-07-07 2022-06-21 Sabic Global Technologies B.V. Polyethylene composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB872197A (en) * 1957-08-08 1961-07-05 Hoechst Ag Process for improving polyolefines
GB1194968A (en) * 1967-08-04 1970-06-17 Hercules Inc Stabilization of Olefin Polymers againts Copper-Induced Degradation
EP0048562A1 (fr) * 1980-09-18 1982-03-31 Uniroyal, Inc. Combinaison de stabilisants pour matières organiques à base de dérivés d'oxamides phénoliques et de phosphites
EP0151327A1 (fr) * 1984-01-06 1985-08-14 SOLVAY & Cie (Société Anonyme) Compositions stabilisées à base de polymères d'alpha-oléfines
JPH06278184A (ja) * 1993-03-29 1994-10-04 Hitachi Cable Ltd プラスチックチューブ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB872197A (en) * 1957-08-08 1961-07-05 Hoechst Ag Process for improving polyolefines
GB1194968A (en) * 1967-08-04 1970-06-17 Hercules Inc Stabilization of Olefin Polymers againts Copper-Induced Degradation
EP0048562A1 (fr) * 1980-09-18 1982-03-31 Uniroyal, Inc. Combinaison de stabilisants pour matières organiques à base de dérivés d'oxamides phénoliques et de phosphites
EP0151327A1 (fr) * 1984-01-06 1985-08-14 SOLVAY & Cie (Société Anonyme) Compositions stabilisées à base de polymères d'alpha-oléfines
JPH06278184A (ja) * 1993-03-29 1994-10-04 Hitachi Cable Ltd プラスチックチューブ

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9444, Derwent World Patents Index; Class A17, AN 94-354236, XP002089799 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11365307B2 (en) * 2017-07-07 2022-06-21 Sabic Global Technologies B.V. Polyethylene composition

Also Published As

Publication number Publication date
AU9560398A (en) 1999-05-03

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