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US20100016481A1 - Polyolefin composition with increased resistance to cio2-containing water - Google Patents

Polyolefin composition with increased resistance to cio2-containing water Download PDF

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Publication number
US20100016481A1
US20100016481A1 US12/443,645 US44364507A US2010016481A1 US 20100016481 A1 US20100016481 A1 US 20100016481A1 US 44364507 A US44364507 A US 44364507A US 2010016481 A1 US2010016481 A1 US 2010016481A1
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Prior art keywords
polyolefin composition
substituted
antioxidant
hydrocarbyl radical
clo
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US12/443,645
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Per-Ola Hagstrand
Perry Nylander
Mats Bäckman
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Borealis Technology Oy
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Borealis Technology Oy
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    • 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
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes

Definitions

  • the present invention relates to a polyolefin composition with increased resistance to degradation caused by ClO 2 -containing water and to a pipe made of such a polyolefin composition.
  • the present invention further relates to the use of the polyolefin composition for the production of a pipe and to the use of a specific antioxidant for increasing the resistance of the polyolefin composition against degradation caused by contact with ClO 2 -containing water.
  • chlorinated water denotes water which contains chlorine, i.e. the following three forms in equation which is dependent on the pH value and known to the person skilled in the art: Cl 2 , HOCl, and ClO ⁇ .
  • Chlorinated water can be produced by adding chlorine gas (Cl 2 ) or sodium hypochlorite (NaOCl) to water.
  • antioxidants In order to increase the lifetime of polyolefin pipes exposed to chlorinated water, it is known to add various antioxidants to the composition the pipe is made of. Suitable and often used antioxidants are pentaerythrityl-tetrakis(3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate (CAS No. 6683-19-8, “Irganox 1010”), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenyl)benzene (CAS No. 1709-70-2, “Irganox 1330”) and tris(2,4-di-t-butylphenyl)phosphite (CAS No. 31570-04-4, “Irgafos 168”).
  • chlorine dioxide a more effective disinfectant used in water is chlorine dioxide, ClO 2 .
  • the use of chlorine dioxide has been seen as favourable for pipes made of a polyolefin composition, as it does not react with the carbon-carbon main chain of the polyolefin.
  • ClO 2 readily reacts with many antioxidants used in pipe compositions and therefore indirectly increases the aging of the polymers and hence the pipes made thereof.
  • antioxidants used in polyolefin compositions for pipes known to provide a good resistance to chlorinated water do not provide satisfactory resistance against water containing chlorine dioxide.
  • a more efficient antioxidant which provides a better protection against ClO 2 -containing water to a polyolefin composition, and thus allows for a longer lifetime of e.g. a pipe, made of a polyolefin composition containing such an antioxidant.
  • a further important issue as regards the presence of antioxidants in polyolefin compositions is the aim to avoid contamination of media transported e.g. in a pipe made of such a polyolefin composition. This is particularly important in case of a pipe transporting drinking water.
  • it is desirable that the antioxidant used has a low tendency to extraction by the water transported in the pipe.
  • the object of the present invention to provide a polyolefin composition with increased resistance to degradation caused by ClO 2 -containing water and particularly to provide a pipe with increased lifetime when exposed to ClO 2 -containing water. Still further, it is an object of the invention that the above objects are achieved by using an amount as small as possible of an antioxidant and that the antioxidant used has a low tendency for extraction by the water transported in a pipe made of such a polyolefin composition.
  • the present invention is based on the surprising finding that the above mentioned objects can be achieved by a polyolefin composition comprising a polyolefin base resin and a specifically selected antioxidant.
  • the present invention provides a polyolefin composition
  • a polyolefin composition comprising a polyolefin base resin and an antioxidant characterized in that said polyolefin composition has a lifetime of at least 200 h in a test measuring the resistance against ClO 2 -containing water at 90° C. and at a concentration of ClO 2 of 4 ppm wherein the equipment used is according to ASTM F2263-03.
  • compositions of the invention show a superior life time in said ClO 2 water test, and such a superior lifetime and hence improved resistance against water containing ClO 2 is not obtained by the use of common antioxidants used for improving the resistance of a polyolefin composition against chlorine-containing water in usual amounts.
  • base resin denotes the entirety of polymeric components in the polyolefin composition according to the invention, usually making up at least 90 wt % of the total composition.
  • the favourable effect of the antioxidants according to the present invention is not dependent on the type of olefin base resin used.
  • the base resin may therefore be any polyolefin composition.
  • the antioxidant is selected from
  • At least one of the substituents R, R′ and/or R′′ of the phenol comprises at least one sulphur heteroatom(s).
  • At least one of the heteroatoms preferably a sulphur heteroatom, is directly attached to at least one phenol group.
  • the heteroatom preferably sulphur
  • group R is present in group R, and preferably is directly attached to at least one phenol group.
  • X 2 is a hydroxy group.
  • R′ is a hydrogen atom or a aliphatic hydrocarbyl radical, preferably with up to 10 carbon atoms. Most preferably, R′ is a hydrogen atom.
  • R′′ in formula I preferably is a hydrogen atom or an aliphatic hydrocarbyl radical, preferably with up to 10 carbon atoms. Most preferably, R′′ is a t-butyl group.
  • X 1 is a hydrogen atom or an aliphatic hydrocarbyl radical, preferably with up to 10 carbon atoms. Most preferably, X 1 is a methyl radical.
  • X 3 in formula I preferably is a hydrogen atom or an aliphatic hydrocarbyl radical, preferably with up to 10 carbon atoms. Most preferably, X 3 is a hydrogen atom.
  • R in the phenolic antioxidant according to formula I is an aliphatic hydrocarbyl group, preferably comprising a heteroatom, with preferably up to 10 atoms, or is a heteroatom selected from the group of S, N and P. More preferably, R is a S, N, or P atom, and most preferably, R is a S atom.
  • n 2 or 3.
  • R 1 , R 2 , R 3 and R 4 are the same.
  • R 1 , R 2 , R 3 and R 4 are aliphatic hydrocarbyl radicals with one to ten carbon atoms each. Still more preferably, all four radicals are a methyl group.
  • R 6 is hydrogen
  • R a or R b independently are an aliphatic hydrocarbyl radical, optionally comprising heteroatoms, preferably comprising from 4 to 50 C-atoms, more preferably from 10 to 30 C-atoms.
  • R a or R b comprise at least one ester group.
  • the polyolefin composition comprises only antioxidants selected from only one of groups a), b) and c), or any mixture thereof.
  • the polyolefin composition comprises only antioxidants of one of groups a), b) or c), and more preferably comprises one antioxidant compound only.
  • the amount of the antioxidant in the polyolefin composition is preferably 5000 ppm or less, more preferably 3500 ppm or less, still more preferably 2500 ppm or less and particularly preferred is 1000 ppm or less.
  • the composition will contain the antioxidant in an amount of at least 50 ppm, more preferably of at least 100 ppm.
  • antioxidants of the phenols of group a) wherein the heteroatom in the aliphatic part is sulphur examples include 2,2′-Thiodiethylene bis(3,5-di-t-butyl-4-hydroxyphenyl)propionate (CAS No. 41484-35-9, “Irganox 1035”), 4,4′-Thiobis(2-t-butyl-5-methylphenol) (CAS No. 96-69-5, “Lowinox TBM-6P”), 6,6′-di-t-butyl-2,2′-thiodi-p-cresol (CAS No. 90-66-4, “Irganox 1081”).
  • antioxidants of the phenols of group a) wherein the heteroatom in the aliphatic part is phosphorus are calcium (3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate) (CAS No. 65140-91-2, “Irganox 1425”) and 3,5-Bis(1,1-dimethylethyl)-4-hydroxybenzyl diethyl-phosphonate (CAS No. 976-56-7, “Irganox 1222”).
  • antioxidants of the phenols of group a) wherein the heteroatom in the aliphatic part is nitrogen are 1,3,5-Tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)isocyanurate (CAS No. 27676-62-6, “Irganox 3114”), N,N′-Hexamethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide] (CAS No. 23128-74-7, “Irganox 1098”) and N,N′-Bis(3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionyl)hydrazine (CAS No. 32687-78-8, “Irganox MD 1024”).
  • antioxidants of the amines of group b) are bis(2,2,6,6-tetramethyl-4-piperidyl)decanediate (“Tinuvin 770”, CAS No. 52829-07-9), poly[1-(2′-hydroxyethyl)-4-hydroxy-2,2,6,6-tetra-methylpiperidylsuccinate] (CAS No.
  • Tivin 622 and poly((6-((1,1,3,3-tetramethylbutyl)amino)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)(1,6-hexanediyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)) (CAS No. 71878-19-8, “Chimassorb 944”).
  • An example for a preferred antioxidant of the sulphur-containing compounds of group c) is di-stearyl-thio-di-propionate (CAS No. 693-36-7, “Arenox DS” or “Irganox PS-802 FL”).
  • the polyolefin base resin of the composition of the invention comprises a polyethylene, i.e. an ethylene homo- or copolymer.
  • the base resin comprises two or more polyolefin, more preferably polyethylene, fractions with different weight average molecular weight.
  • Such resins usually are denoted as multimodal resins.
  • compositions comprising multimodal resins are frequently used e.g. for the production of pipes due to their favourable physical and chemical properties as e.g. mechanical strength, corrosion resistance and long-term stability.
  • Such compositions are described e.g. in EP 0 739 937 and WO 02/102891.
  • molecular weight used herein generally denotes the weight average molecular weight M w .
  • multimodal a polyethylene composition comprising at least two polyolefin fractions, which have been produced under different polymerization conditions resulting in different weight average molecular weights for the fractions.
  • multi relates to the number of different polymer fractions the composition is consisting of.
  • a composition consisting of two fractions only is called “bimodal”.
  • the form of the molecular weight distribution curve i.e. the appearance of the graph of the polymer weight fraction as function of its molecular weight, of such a multimodal polyethylene will show two or more maxima or at least be distinctly broadened in comparison with the curves for the individual fractions.
  • the polymer fractions produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight.
  • the individual curves from these fractions are superimposed into the molecular weight distribution curve for the total resulting polymer product, usually yielding a curve with two or more distinct maxima.
  • fraction (A) the fraction having a lower weight average molecular weight
  • fraction (B) the fraction having a lower weight average molecular weight
  • Fraction (A) preferably is an ethylene homopolymer.
  • Fraction (B) of the polyethylene composition preferably is an ethylene copolymer, and preferably comprises at least 0.1 mol % of at least one alpha-olefin comonomer.
  • the amount of comonomer is preferably at most 14 mol %.
  • the base resin of the polyethylene composition preferably comprises at least 0.1 mol %, more preferably at least 0.3 mol %, and still more preferably at least 0.7 mol % of at least one alpha-olefin comonomer.
  • the amount of comonomer is preferably at most 7.0 mol %, more preferably at most 6.0 mol %, and still more preferably at most 5.0 mol %.
  • an alpha-olefin comonomer preferably an alpha-olefin having from 4 to 8 carbon atoms is used. Still more preferably an alpha-olefin selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene is used.
  • the polyolefin base resin preferably has an MFR 5 (190° C., 5 kg) of from 0.1 to 1.2 g/10 min, more preferably from 0.2 to 0.8 g/10 min, and most preferably from 0.25 to 0.6 g/10 min.
  • the density of the base resin preferably is from 930 to 960 kg/m 3 , more preferably is from 935 to 958 kg/m 3 , and most preferably is from 938 to 952 kg/m 3 .
  • polyolefins for example carbon black
  • pigments for example carbon black
  • stabilizers for example carbon black
  • antacids and/or anti-UVs for example carbon black
  • antistatic agents and utilization agents such as processing aid agents
  • the amount of such additives usually is 10 wt. % or below.
  • the polymerization catalysts for the production of the base resin include coordination catalysts of a transition metal, such as Ziegler-Natta (ZN), metallocenes, non-metallocenes, Cr-catalysts etc.
  • the catalyst may be supported, e.g. with conventional supports including silica, Al-containing supports and magnesium dichloride based supports.
  • the catalyst is a ZN catalyst, more preferably the catalyst is a non-silica supported ZN catalyst, and most preferably a MgCl 2 -based ZN catalyst.
  • the Ziegler-Natta catalyst further preferably comprises a group 4 (group numbering according to new IUPAC system) metal compound, preferably titanium, magnesium dichloride and aluminium.
  • the catalyst may be commercially available or be produced in accordance or analogously to the literature.
  • reference is made to WO2004055068 and WO2004055069 of Borealis and EP 0 810 235.
  • the content of these documents in its entirety is incorporated herein by reference, in particular concerning the general and all preferred embodiments of the catalysts described therein as well as the methods for the production of the catalysts.
  • Particularly preferred Ziegler-Natta catalysts are described in EP 0 810 235.
  • the composition preferably is produced in a process comprising a compounding step, wherein the base resin which is typically obtained as a base resin powder from the reactor, together with the antioxidant and optionally other additives is extruded in an extruder to yield the composition of the invention.
  • the improved resistance of the polyolefin composition against degradation caused by contact with ClO 2 -containing water is measured at 90° C. and at a concentration of ClO 2 of 4 ppm wherein the equipment used is according to ASTM F2263-03.
  • a pipe made of the polyolefin composition of the invention is capable of obtaining a lifetime of at least 200 h, more preferably of at least 220 h, in this test.
  • the present invention is also directed to a pipe comprising a polyolefin composition according to the invention including any of the preferred embodiments described above.
  • the pipe is preferably for transportation of drinking water, especially drinking water containing ClO 2 .
  • the present invention is also directed to the use of a polyolefin composition according to the invention for the production of a pipe. Still further, the present invention is directed to the use of such a pipe for drinking water transportation.
  • the present invention is also directed to the use of an antioxidant for increasing the resistance of a polyolefin composition against degradation caused by contact with ClO 2 -containing water.
  • the antioxidant is defined as described above including the preferred embodiments.
  • Density is measured according to ISO 1183. Sample preparation is done in accordance with ISO 1872/2B.
  • the melt flow rate is determined according to ISO 1133 and is indicated in g/10 min.
  • the MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.
  • the MFR is determined at 190° C. for polyethylene and may be determined at different loadings such as 2.16 kg (MFR 2 ), 5.00 kg (MFR 5 ) or 21.6 kg (MFR 21 ).
  • FRR flow rate ratio
  • a circulation loop is used for water which contains ClO 2 .
  • the concentration of ClO 2 in the water is 4.0 ⁇ 0.1 ppm.
  • the pH of the water is 6.8 ⁇ 0.2.
  • the temperature of the water is 90 ⁇ 1° C.
  • the hoop stress applied to the pipe is about 1.7 MPa.
  • the oxidation reduction potential (ORP) is 740 mV and is measured frequently.
  • the flow volume is 23 l/h at a flow velocity of about 0.13 m/s and a fluid pressure of 6.5 bar.
  • the free pipe length is 250 mm, the outer diameter of the pipe is 12 mm and the thickness of the wall is 2 mm. In the tests two pipes of each material are tested in series, the results given are the average of the two values measured.
  • the circulation loop used for ClO 2 testing is made from inert materials (e.g. titanium, PVDF (Polyvinylidene difluoride), PTFE (Polytetrafluoro-ethylene) to avoid contamination of the test fluid.
  • inert materials e.g. titanium, PVDF (Polyvinylidene difluoride), PTFE (Polytetrafluoro-ethylene) to avoid contamination of the test fluid.
  • the fittings are of PVDF.
  • the test fluid is continuously purified in three steps to avoid any contamination: 1. active carbon filter, 2. particle filter, 3. reverse osmosis.
  • the internal environment is the above-mentioned solution of ClO 2 in water, the external environment is air.
  • the ClO 2 is generated directly at the site using a commercial ClO 2 -generator from Prominent following the equation:
  • the mechanism for feeding the stock solutions (NaClO 2 and HCl) to the process are monitored to maintain a consistent ratio of chemicals.
  • Sample preparation The polymer pellets are ground and 5 g of the ground polymer is extracted in 50 ml of cyclohexane at a temperature of 81° C. for 2 hours. If needed, cyclohexane is then added to exact 50 ml again. The solution is cooled down in room temperature and thereafter the polymer is precipitated with 50 ml iso-propanol. A suitable amount of the solution is filtered and injected into an HPLC equipment.
  • the HPLC measurement can e.g. be performed with a reversed phase C-18 column and methanol and water as mobile phase, for example in a ratio of 85:15.
  • a UV detector can be used, wavelength 280 nm for Irganox 1010, Irgafos 168 and Irganox 1330 and 220 nm for Lowinox TBM-6P.
  • the quantification is made using calibration curves in a conventional manner.
  • Polyethylene compositions for the testing of pipes were produced from commercially available polyethylene resins.
  • the properties of the base resins used, as well as the additives which were added to the base resins to yield the polyethylene compositions used for pipe production are given in Table 1.
  • Table 1 also the results of the lifetime tests in ClO 2 -containing and chlorinated water are given.
  • Example 1 as antioxidant 4,4′-Thiobis(2-t-butyl-5-methylphenol) (CAS No. 96-69-5, Lowinox TBM-6P) was used.
  • Comparative Example 2 a typical mixture of conventional antioxidants as used to provide pipes with good resistance to chlorinated water in usual amounts has been used.
  • Example 1 the total amount of antioxidant is much less in Example 1 than in Comparative Example 2, and that in Example 1 only one antioxidant is used whereas in Comparative Example 2 a mixture of two different antioxidants was used.

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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)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The present invention relates to a polyolefin composition comprising a polyolefin base resin and an antioxidant, characterized in that said polyolefin composition has a lifetime of at least 200 h in a test measuring the resistance against ClO2-containing water at 90° C., and at a concentration of ClO2 of 4 ppm wherein the equipment used is according to ASTM F2263-03. The present invention further relates to a pipe comprising the polyolefin composition according to the invention, to the use of the polyolefin composition for the production of a pipe, and to the use of a particularly selected antioxidant for increasing the resistance of a polyolefin composition against degradation caused by contact with ClO2-containing water.

Description

  • The present invention relates to a polyolefin composition with increased resistance to degradation caused by ClO2-containing water and to a pipe made of such a polyolefin composition. The present invention further relates to the use of the polyolefin composition for the production of a pipe and to the use of a specific antioxidant for increasing the resistance of the polyolefin composition against degradation caused by contact with ClO2-containing water.
  • It is known that chlorine in different molecular forms is used as disinfectant in water treatment to prevent spread of infectious diseases. It is also known that most materials, including many polymers such as polyolefins, age in chlorinated water. Results from pressure testing in laboratories and experience from the field have shown that high concentration of chlorine in water can cause early brittle fracture in polyolefin pipes.
  • The term “chlorinated water” as used herein denotes water which contains chlorine, i.e. the following three forms in equation which is dependent on the pH value and known to the person skilled in the art: Cl2, HOCl, and ClO−. Chlorinated water can be produced by adding chlorine gas (Cl2) or sodium hypochlorite (NaOCl) to water.
  • In order to increase the lifetime of polyolefin pipes exposed to chlorinated water, it is known to add various antioxidants to the composition the pipe is made of. Suitable and often used antioxidants are pentaerythrityl-tetrakis(3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate (CAS No. 6683-19-8, “Irganox 1010”), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenyl)benzene (CAS No. 1709-70-2, “Irganox 1330”) and tris(2,4-di-t-butylphenyl)phosphite (CAS No. 31570-04-4, “Irgafos 168”).
  • However, a more effective disinfectant used in water is chlorine dioxide, ClO2. The use of chlorine dioxide has been seen as favourable for pipes made of a polyolefin composition, as it does not react with the carbon-carbon main chain of the polyolefin. However, it has been found that ClO2 readily reacts with many antioxidants used in pipe compositions and therefore indirectly increases the aging of the polymers and hence the pipes made thereof.
  • It has been found that antioxidants used in polyolefin compositions for pipes known to provide a good resistance to chlorinated water do not provide satisfactory resistance against water containing chlorine dioxide. Thus, there is the need for a more efficient antioxidant which provides a better protection against ClO2-containing water to a polyolefin composition, and thus allows for a longer lifetime of e.g. a pipe, made of a polyolefin composition containing such an antioxidant.
  • A further important issue as regards the presence of antioxidants in polyolefin compositions is the aim to avoid contamination of media transported e.g. in a pipe made of such a polyolefin composition. This is particularly important in case of a pipe transporting drinking water. Generally speaking, it is preferred to use as low concentrations of antioxidant as possible in order to lower the amount of antioxidant which may possibly be extracted by the water transported in the pipe. Further in this context, it is desirable that the antioxidant used has a low tendency to extraction by the water transported in the pipe.
  • Still further, from an environmental as well as from an economical point of view, it is also desirable to use preferably one antioxidant only, i.e. it is desirable to avoid mixtures of antioxidants.
  • Accordingly, it is the object of the present invention to provide a polyolefin composition with increased resistance to degradation caused by ClO2-containing water and particularly to provide a pipe with increased lifetime when exposed to ClO2-containing water. Still further, it is an object of the invention that the above objects are achieved by using an amount as small as possible of an antioxidant and that the antioxidant used has a low tendency for extraction by the water transported in a pipe made of such a polyolefin composition.
  • The present invention is based on the surprising finding that the above mentioned objects can be achieved by a polyolefin composition comprising a polyolefin base resin and a specifically selected antioxidant.
  • Accordingly, the present invention provides a polyolefin composition comprising a polyolefin base resin and an antioxidant characterized in that said polyolefin composition has a lifetime of at least 200 h in a test measuring the resistance against ClO2-containing water at 90° C. and at a concentration of ClO2 of 4 ppm wherein the equipment used is according to ASTM F2263-03.
  • As is e.g. shown in the examples, the compositions of the invention show a superior life time in said ClO2 water test, and such a superior lifetime and hence improved resistance against water containing ClO2 is not obtained by the use of common antioxidants used for improving the resistance of a polyolefin composition against chlorine-containing water in usual amounts.
  • The term “base resin” denotes the entirety of polymeric components in the polyolefin composition according to the invention, usually making up at least 90 wt % of the total composition.
  • The favourable effect of the antioxidants according to the present invention is not dependent on the type of olefin base resin used. The base resin may therefore be any polyolefin composition.
  • In a preferred embodiment, the antioxidant is selected from
      • a) the group of phenols according to formula I:
  • Figure US20100016481A1-20100121-C00001
        • wherein
        • R is a non-substituted or substituted aliphatic or aromatic hydrocarbyl radical which may comprise heteroatoms or R is a heteroatom,
        • R′ and R″ independently are a non-substituted or substituted hydrocarbyl radical which may comprise heteroatoms or H,
        • X1, X2 and X3 independently are a non-substituted or substituted hydrocarbyl radical which may comprise heteroatoms or H or OH, with at least X1, X2 or X3 being OH,
        • n is 1 to 4, and
        • at least one of the substituents R, R′ and/or R″ of the phenol comprises at least one sulphur, phosphorus and/or nitrogen heteroatom(s),
      • or is selected from
      • b) the amine compounds according to formula II:
  • Figure US20100016481A1-20100121-C00002
        • wherein R1, R2, R3, R4, R5 and R6 independently are hydrogen or an aliphatic or aromatic hydrocarbyl radical, optionally comprising heteroatoms,
      • or is selected from
      • c) the sulphur-containing compounds according to formula III:

  • Ra—S—Rb,
        • wherein Ra and Rb independently are an aliphatic or aromatic hydrocarbyl radical, optionally comprising heteroatoms.
  • More preferably, in the antioxidant of said group of phenols a) according to formula I at least one of the substituents R, R′ and/or R″ of the phenol comprises at least one sulphur heteroatom(s).
  • In a preferred embodiment of the antioxidant of group a) according to formula I, at least one of the heteroatoms, preferably a sulphur heteroatom, is directly attached to at least one phenol group.
  • Furthermore, preferably, the heteroatom, preferably sulphur, is present in group R, and preferably is directly attached to at least one phenol group.
  • In the phenol antioxidants of group a) according to formula I preferably X2 is a hydroxy group.
  • Furthermore, in formula I preferably R′ is a hydrogen atom or a aliphatic hydrocarbyl radical, preferably with up to 10 carbon atoms. Most preferably, R′ is a hydrogen atom.
  • R″ in formula I preferably is a hydrogen atom or an aliphatic hydrocarbyl radical, preferably with up to 10 carbon atoms. Most preferably, R″ is a t-butyl group.
  • Still further, preferably in formula I, X1 is a hydrogen atom or an aliphatic hydrocarbyl radical, preferably with up to 10 carbon atoms. Most preferably, X1 is a methyl radical.
  • X3 in formula I preferably is a hydrogen atom or an aliphatic hydrocarbyl radical, preferably with up to 10 carbon atoms. Most preferably, X3 is a hydrogen atom.
  • Preferably, R in the phenolic antioxidant according to formula I is an aliphatic hydrocarbyl group, preferably comprising a heteroatom, with preferably up to 10 atoms, or is a heteroatom selected from the group of S, N and P. More preferably, R is a S, N, or P atom, and most preferably, R is a S atom.
  • Furthermore, preferably n is 2 or 3.
  • In the amine antioxidants of group b) according to formula II preferably R1, R2, R3 and R4 are the same.
  • Further preferred, R1, R2, R3 and R4 are aliphatic hydrocarbyl radicals with one to ten carbon atoms each. Still more preferably, all four radicals are a methyl group.
  • In a further preferred embodiment R6 is hydrogen.
  • In the sulphur containing antioxidants of group c) according to formula III preferably Ra or Rb, more preferably Ra and Rb, independently are an aliphatic hydrocarbyl radical, optionally comprising heteroatoms, preferably comprising from 4 to 50 C-atoms, more preferably from 10 to 30 C-atoms.
  • Furthermore, preferably Ra or Rb, more preferably Ra and Rb, comprise at least one ester group.
  • It is within the scope of the invention that the polyolefin composition comprises only antioxidants selected from only one of groups a), b) and c), or any mixture thereof.
  • However, according to a preferred embodiment of the present invention, the polyolefin composition comprises only antioxidants of one of groups a), b) or c), and more preferably comprises one antioxidant compound only.
  • The amount of the antioxidant in the polyolefin composition is preferably 5000 ppm or less, more preferably 3500 ppm or less, still more preferably 2500 ppm or less and particularly preferred is 1000 ppm or less.
  • Usually, the composition will contain the antioxidant in an amount of at least 50 ppm, more preferably of at least 100 ppm.
  • Examples for preferred antioxidants of the phenols of group a) wherein the heteroatom in the aliphatic part is sulphur are 2,2′-Thiodiethylene bis(3,5-di-t-butyl-4-hydroxyphenyl)propionate (CAS No. 41484-35-9, “Irganox 1035”), 4,4′-Thiobis(2-t-butyl-5-methylphenol) (CAS No. 96-69-5, “Lowinox TBM-6P”), 6,6′-di-t-butyl-2,2′-thiodi-p-cresol (CAS No. 90-66-4, “Irganox 1081”).
  • Examples for preferred antioxidants of the phenols of group a) wherein the heteroatom in the aliphatic part is phosphorus are calcium (3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate) (CAS No. 65140-91-2, “Irganox 1425”) and 3,5-Bis(1,1-dimethylethyl)-4-hydroxybenzyl diethyl-phosphonate (CAS No. 976-56-7, “Irganox 1222”).
  • Examples for preferred antioxidants of the phenols of group a) wherein the heteroatom in the aliphatic part is nitrogen are 1,3,5-Tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)isocyanurate (CAS No. 27676-62-6, “Irganox 3114”), N,N′-Hexamethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide] (CAS No. 23128-74-7, “Irganox 1098”) and N,N′-Bis(3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionyl)hydrazine (CAS No. 32687-78-8, “Irganox MD 1024”).
  • Examples for preferred antioxidants of the amines of group b) are bis(2,2,6,6-tetramethyl-4-piperidyl)decanediate (“Tinuvin 770”, CAS No. 52829-07-9), poly[1-(2′-hydroxyethyl)-4-hydroxy-2,2,6,6-tetra-methylpiperidylsuccinate] (CAS No. 65447-77-0, “Tinuvin 622”) and poly((6-((1,1,3,3-tetramethylbutyl)amino)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)(1,6-hexanediyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)) (CAS No. 71878-19-8, “Chimassorb 944”).
  • An example for a preferred antioxidant of the sulphur-containing compounds of group c) is di-stearyl-thio-di-propionate (CAS No. 693-36-7, “Arenox DS” or “Irganox PS-802 FL”).
  • Preferably, the polyolefin base resin of the composition of the invention comprises a polyethylene, i.e. an ethylene homo- or copolymer.
  • In one embodiment of the invention the base resin comprises two or more polyolefin, more preferably polyethylene, fractions with different weight average molecular weight. Such resins usually are denoted as multimodal resins.
  • Polyolefin, in particular polyethylene, compositions comprising multimodal resins are frequently used e.g. for the production of pipes due to their favourable physical and chemical properties as e.g. mechanical strength, corrosion resistance and long-term stability. Such compositions are described e.g. in EP 0 739 937 and WO 02/102891. The term molecular weight used herein generally denotes the weight average molecular weight Mw.
  • As mentioned, usually a polyethylene composition comprising at least two polyolefin fractions, which have been produced under different polymerization conditions resulting in different weight average molecular weights for the fractions, is referred to as “multimodal”. The prefix “multi” relates to the number of different polymer fractions the composition is consisting of. Thus, for example, a composition consisting of two fractions only is called “bimodal”.
  • The form of the molecular weight distribution curve, i.e. the appearance of the graph of the polymer weight fraction as function of its molecular weight, of such a multimodal polyethylene will show two or more maxima or at least be distinctly broadened in comparison with the curves for the individual fractions.
  • For example, if a polymer is produced in a sequential multistage process, utilizing reactors coupled in series and using different conditions in each reactor, the polymer fractions produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight. When the molecular weight distribution curve of such a polymer is recorded, the individual curves from these fractions are superimposed into the molecular weight distribution curve for the total resulting polymer product, usually yielding a curve with two or more distinct maxima.
  • In the preferred embodiment wherein the base resin consists of two polyethylene fractions, the fraction having a lower weight average molecular weight is denoted fraction (A), the other is denoted fraction (B).
  • Fraction (A) preferably is an ethylene homopolymer.
  • Fraction (B) of the polyethylene composition preferably is an ethylene copolymer, and preferably comprises at least 0.1 mol % of at least one alpha-olefin comonomer. The amount of comonomer is preferably at most 14 mol %.
  • In the preferred embodiment wherein the polyolefin composition is a polyethylene composition, the base resin of the polyethylene composition preferably comprises at least 0.1 mol %, more preferably at least 0.3 mol %, and still more preferably at least 0.7 mol % of at least one alpha-olefin comonomer. The amount of comonomer is preferably at most 7.0 mol %, more preferably at most 6.0 mol %, and still more preferably at most 5.0 mol %.
  • As an alpha-olefin comonomer, preferably an alpha-olefin having from 4 to 8 carbon atoms is used. Still more preferably an alpha-olefin selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene is used.
  • The polyolefin base resin preferably has an MFR5 (190° C., 5 kg) of from 0.1 to 1.2 g/10 min, more preferably from 0.2 to 0.8 g/10 min, and most preferably from 0.25 to 0.6 g/10 min.
  • The density of the base resin preferably is from 930 to 960 kg/m3, more preferably is from 935 to 958 kg/m3, and most preferably is from 938 to 952 kg/m3.
  • In addition to the base resin and the antioxidant, usual additives for utilization with polyolefins, such as pigments (for example carbon black), stabilizers, antacids and/or anti-UVs, antistatic agents and utilization agents (such as processing aid agents) may be present in the polyolefin composition.
  • The amount of such additives usually is 10 wt. % or below.
  • The polymerization catalysts for the production of the base resin include coordination catalysts of a transition metal, such as Ziegler-Natta (ZN), metallocenes, non-metallocenes, Cr-catalysts etc. The catalyst may be supported, e.g. with conventional supports including silica, Al-containing supports and magnesium dichloride based supports. Preferably the catalyst is a ZN catalyst, more preferably the catalyst is a non-silica supported ZN catalyst, and most preferably a MgCl2-based ZN catalyst.
  • The Ziegler-Natta catalyst further preferably comprises a group 4 (group numbering according to new IUPAC system) metal compound, preferably titanium, magnesium dichloride and aluminium.
  • The catalyst may be commercially available or be produced in accordance or analogously to the literature. For the preparation of the preferable catalyst usable in the invention reference is made to WO2004055068 and WO2004055069 of Borealis and EP 0 810 235. The content of these documents in its entirety is incorporated herein by reference, in particular concerning the general and all preferred embodiments of the catalysts described therein as well as the methods for the production of the catalysts. Particularly preferred Ziegler-Natta catalysts are described in EP 0 810 235.
  • The composition preferably is produced in a process comprising a compounding step, wherein the base resin which is typically obtained as a base resin powder from the reactor, together with the antioxidant and optionally other additives is extruded in an extruder to yield the composition of the invention.
  • The improved resistance of the polyolefin composition against degradation caused by contact with ClO2-containing water is measured at 90° C. and at a concentration of ClO2 of 4 ppm wherein the equipment used is according to ASTM F2263-03. A pipe made of the polyolefin composition of the invention is capable of obtaining a lifetime of at least 200 h, more preferably of at least 220 h, in this test.
  • Accordingly, the present invention is also directed to a pipe comprising a polyolefin composition according to the invention including any of the preferred embodiments described above. The pipe is preferably for transportation of drinking water, especially drinking water containing ClO2.
  • The present invention is also directed to the use of a polyolefin composition according to the invention for the production of a pipe. Still further, the present invention is directed to the use of such a pipe for drinking water transportation.
  • Still further, the present invention is also directed to the use of an antioxidant for increasing the resistance of a polyolefin composition against degradation caused by contact with ClO2-containing water. The antioxidant is defined as described above including the preferred embodiments.
    • EXAMPLES
  • 1. Definitions and Measurement Methods
  • a) Density
  • Density is measured according to ISO 1183. Sample preparation is done in accordance with ISO 1872/2B.
  • b) Melt Flow Rate/Flow Rate Ratio
  • The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g/10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR is determined at 190° C. for polyethylene and may be determined at different loadings such as 2.16 kg (MFR2), 5.00 kg (MFR5) or 21.6 kg (MFR21).
  • The quantity FRR (flow rate ratio) is an indication of molecular weight distribution and denotes the ratio of flow rates at different loadings. Thus, FRR21/5 denotes the value of MFR21/MFR5.
  • c) Measurement of Lifetime of Pipes in Contact with ClO2
  • No standard exists yet for evaluating the resistance of pipes comprising a polyethylene composition to ClO2-containing water. However, there is a standard for measuring the resistance to chlorinated water: ASTM F2263-03, “Standard test method for evaluating the oxidative resistance of Polyethylene (PE) pipe to chlorinated water”. The lifetime of the pipes is tested accordingly with an equipment according to ASTM F2263-03. However, ClO2 is applied instead of chlorine (Cl2, NaOCl).
  • A circulation loop is used for water which contains ClO2. The concentration of ClO2 in the water is 4.0±0.1 ppm. The pH of the water is 6.8±0.2. The temperature of the water is 90±1° C. The hoop stress applied to the pipe is about 1.7 MPa. The oxidation reduction potential (ORP) is 740 mV and is measured frequently. The flow volume is 23 l/h at a flow velocity of about 0.13 m/s and a fluid pressure of 6.5 bar. The free pipe length is 250 mm, the outer diameter of the pipe is 12 mm and the thickness of the wall is 2 mm. In the tests two pipes of each material are tested in series, the results given are the average of the two values measured.
  • The circulation loop used for ClO2 testing is made from inert materials (e.g. titanium, PVDF (Polyvinylidene difluoride), PTFE (Polytetrafluoro-ethylene) to avoid contamination of the test fluid. The fittings are of PVDF. The test fluid is continuously purified in three steps to avoid any contamination: 1. active carbon filter, 2. particle filter, 3. reverse osmosis.
  • The internal environment is the above-mentioned solution of ClO2 in water, the external environment is air.
  • The ClO2 is generated directly at the site using a commercial ClO2-generator from Prominent following the equation:

  • 5 NaClO2+4HCl→4 ClO2+2 H2O+5 NaCl
  • The mechanism for feeding the stock solutions (NaClO2 and HCl) to the process are monitored to maintain a consistent ratio of chemicals.
  • All tests were carried out at Bodycote Polymer AB, Nyköping, Sweden.
  • d) Measurement of Lifetime of Pipes in Contact with Chlorinated Water
  • The lifetime measurements for pipes in contact with chlorinated water were performed in accordance with ASTM F2263-03. All tests were carried out at Bodycote Polymer AB, Nyköping, Sweden.
  • e) Content of Antioxidant
  • Sample preparation: The polymer pellets are ground and 5 g of the ground polymer is extracted in 50 ml of cyclohexane at a temperature of 81° C. for 2 hours. If needed, cyclohexane is then added to exact 50 ml again. The solution is cooled down in room temperature and thereafter the polymer is precipitated with 50 ml iso-propanol. A suitable amount of the solution is filtered and injected into an HPLC equipment.
  • The HPLC measurement can e.g. be performed with a reversed phase C-18 column and methanol and water as mobile phase, for example in a ratio of 85:15. A UV detector can be used, wavelength 280 nm for Irganox 1010, Irgafos 168 and Irganox 1330 and 220 nm for Lowinox TBM-6P. The quantification is made using calibration curves in a conventional manner.
  • 2. Lifetime of Pipes Comprising Different Antioxidants
  • Polyethylene compositions for the testing of pipes were produced from commercially available polyethylene resins. The properties of the base resins used, as well as the additives which were added to the base resins to yield the polyethylene compositions used for pipe production are given in Table 1. In Table 1 also the results of the lifetime tests in ClO2-containing and chlorinated water are given.
  • In the Example according to the invention (Example 1) as antioxidant 4,4′-Thiobis(2-t-butyl-5-methylphenol) (CAS No. 96-69-5, Lowinox TBM-6P) was used. In Comparative Example 2, a typical mixture of conventional antioxidants as used to provide pipes with good resistance to chlorinated water in usual amounts has been used.
  • It can be seen from the results in Table 1 that pipes produced from a polyethylene composition comprising conventional antioxidants achieve good results for chlorinated water, however rather bad results for ClO2-containing water (Example 2 (Comp.)). In contrast, the pipe produced from the polyethylene composition comprising antioxidant Lowinox TBM-6P shows a drastically improved performance for ClO2-containing water (Example 1).
  • Furthermore, it can be seen that the total amount of antioxidant is much less in Example 1 than in Comparative Example 2, and that in Example 1 only one antioxidant is used whereas in Comparative Example 2 a mixture of two different antioxidants was used.
  • TABLE 1
    Example 1 2 (Comp.)
    Properties of Base Resin
    MFR5 g/10 min 0.9 0.85
    MFR21 g/10 min 19.8 19
    FRR21/5 22 22.4
    Comonomer hexene-1 hexene-1
    wt. % 3.8 4.2
    Antioxidants Added
    Lowinox TBM-6P ppm 590 —
    Irganox 1010 ppm — 730
    Irgafos 168 ppm — 770
    Total Amount of ppm 590 1500
    Antioxidants
    Other Compounds Added
    Carbon black wt % 2.3 2.3
    Properties of Polyethylene
    Composition
    Density kg/m3 950 951
    Properties of Pipes
    Resistance hours 231 152
    against ClO2-
    containing water
    Resistance hours 847 2370
    against
    chlorinated water

Claims (11)

1. A polyolefin composition comprising a polyolefin base resin and an antioxidant, characterized in that said polyolefin composition has a lifetime of at least 200 h in a test measuring the resistance against ClO2-containing water at 90° C. and at a concentration of ClO2 of 4 ppm wherein the equipment used is according to ASTM F2263-03.
wherein the antioxidant is selected from
a) the group of phenols according to formula I:
Figure US20100016481A1-20100121-C00003
wherein
R is a non-substituted or substituted aliphatic or aromatic hydrocarbyl radical which may comprise heteroatoms or R is a heteroatom,
R′ and R″ independently are a non-substituted or substituted hydrocarbyl radical which may comprise heteroatoms or H,
X1, X2 and X3 independently are a non-substituted or substituted hydrocarbyl radical which may comprise heteroatoms or H or OH, with at least X1, X2 or X3 being OH,
n is 1 to 4, and
at least one of the substituents R, R′ and/or R″ of the phenol comprises at least one sulphur heteroatom(s),
or is selected from
b) the amine compounds according to formula II:
Figure US20100016481A1-20100121-C00004
wherein R1, R2, R3, R4, R5 and R6 independently are hydrogen or an aliphatic or aromatic hydrocarbyl radical, optionally comprising heteroatoms,
or is selected from
c) the sulphur-containing compounds according to formula III:

Ra—S—Rb,
wherein Ra and Rb independently are an aliphatic or aromatic hydrocarbyl radical, optionally comprising heteroatoms.
2. The polyolefin composition according to claim 1 wherein the polyolefin base resin comprises an ethylene homo- or copolymer.
3. The polyolefin composition according to claim 1 wherein the amount of antioxidant in the polyolefin composition is 5000 ppm or less.
4. The polyolefin composition according to claim 3 wherein the amount of antioxidant in the polyolefin composition is 3500 ppm or less.
5. The polyolefin composition according to claim 4 wherein the amount of antioxidant in the polyolefin composition is 2500 ppm or less.
6. A pipe comprising a polyolefin composition according to claim 1.
7-10. (canceled)
11. A method for producing a pipe comprising the polyolefin composition according to claim 1.
12. A method for drinking water transportation comprising a pipe comprising a polyolefin composition according to claim 1.
13. The method according to claim 12 wherein the drinking water contains ClO2.
14. A method for increasing the resistance of a polyolefin composition against degradation caused by contact with ClO2-containing water using an antioxidant selected from
a) the group of phenols according to formula I:
Figure US20100016481A1-20100121-C00005
wherein
R is a non-substituted or substituted aliphatic or aromatic hydrocarbyl radical which may comprise heteroatoms or R is a heteroatom,
R′ and R″ independently are a non-substituted or substituted hydrocarbyl radical which may comprise heteroatoms or H,
X1, X2 and X3 independently are a non-substituted or substituted hydrocarbyl radical which may comprise heteroatoms or H or OH, with at least X1, X2 or X3 being OH,
n is 1 to 4, and
at least one of the substituents R, R′ and/or R″ of the phenol comprises at least one sulphur, phosphorus and/or nitrogen heteroatom(s),
or selected from
b) the amine compounds according to formula II:
Figure US20100016481A1-20100121-C00006
wherein R1, R2, R3, R4, R5 and R6 independently are hydrogen or an aliphatic or aromatic hydrocarbyl radical, optionally comprising heteroatoms,
or selected from
c) the sulphur-containing compounds according to formula III:

Ra—S—Rb,
wherein Ra and Rb independently are an aliphatic or aromatic hydrocarbyl radical, optionally comprising heteroatoms.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140004287A1 (en) * 2011-03-14 2014-01-02 Dow Globel Technologies LLC Ethylene-based compositions
US20150299903A1 (en) * 2014-04-18 2015-10-22 Asahi Kasei Chemicals Corporation Polyethylene Powder for Fiber, Fiber, and Article

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2199330A1 (en) 2008-12-22 2010-06-23 Borealis AG Polyolefin composition for water pipes with good resistance to chlorine dioxide and low migration
EP2199327A1 (en) * 2008-12-22 2010-06-23 Borealis AG Polyolefin composition for water pipes with increased resistance to chlorine dioxide
ES2607784T3 (en) * 2009-05-29 2017-04-04 Uponor Innovation Ab Methods and compositions for producing pipe having improved oxidative resistance
AU2010264811B9 (en) * 2009-06-22 2014-06-05 Borealis Ag Chlorine dioxide resistant polyethylene pipes, their preparation and use
DE202011103017U1 (en) 2011-07-08 2012-10-15 Rehau Ag + Co. Disinfection-resistant multi-layer composite pipe
EP2551294B1 (en) * 2011-07-25 2018-11-07 Borealis AG Use of a polyolefin composition for pipes and fittings with increased resistance to chlorine dioxide
EP2551297B1 (en) * 2011-07-25 2014-03-12 Borealis AG Polyolefin composition with excellent colour and thermal stability as well as oxidation resistance for pipes
ES2530869T3 (en) 2011-12-22 2015-03-06 Borealis Ag Polyolefin composition with increased resistance to degradation caused by chlorine dioxide
EP2725057B2 (en) 2012-10-24 2022-08-24 Borealis AG Use of an acid scavenger to increase the resistance of a polyolefin composition against disinfectant containing water
US20140127438A1 (en) * 2012-11-08 2014-05-08 Robert L. Sherman, Jr. Stabilized high-density polyethylene composition with improved resistance to deterioration and stabilizer system
US20230151223A1 (en) * 2020-03-23 2023-05-18 Sekisui Chemical Co., Ltd. Pipeline member for ultrapure water and polyethylene-based resin composition for pipeline member for ultrapure water

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1087403A (en) * 1963-10-28 1967-10-18 Raychem Corp Improved cross-linked polymer compositions and a process for their manufacture
US3370036A (en) * 1962-07-02 1968-02-20 Phillips Petroleum Co Stabilization of polymers with uv stabilizers and antioxidants
DE1947071A1 (en) * 1968-09-24 1970-09-17 Monsanto Chemicals Electric cables
US4131599A (en) * 1975-05-28 1978-12-26 Sankyo Company, Limited Stabilization of poly(mono-olefins)
US4221699A (en) * 1977-06-14 1980-09-09 Societe Anonyme De Telecommunications Production of extruded polyolefin products
CA1120630A (en) * 1977-10-12 1982-03-23 Olaf E. Larsen Pipe extrusion polymeric blend
JPS5859025A (en) * 1981-09-25 1983-04-07 Tokyo Electric Power Co Inc:The Manufacture of joined section of cable insulated with crosslinked polyethylene
JPH02153955A (en) * 1988-07-07 1990-06-13 Nippon Unicar Co Ltd Polyethylene composition for water pipe
US5266616A (en) * 1991-07-12 1993-11-30 Phillips Petroleum Company Polyolefin resin formulation using organic pigments
JPH11147976A (en) * 1997-11-17 1999-06-02 Toyo Ink Mfg Co Ltd Chlorine-resistant aqueous colored resin composition and water pipe
US6538056B1 (en) * 2000-10-10 2003-03-25 Clariant International Ltd. Polyolefin articles with long-term elevated temperature stability
US6541547B1 (en) * 1995-09-15 2003-04-01 Ciba Specialty Chemicals Corporation Process for stabilization of polyolefins in permanent contact with extracting media
US20030158306A1 (en) * 1998-10-21 2003-08-21 Battiste David R. Phosphite additives in polyolefins
US6680351B1 (en) * 1999-07-20 2004-01-20 Phillips Petroleum Company Phosphite additives in polyolefins
US7238765B2 (en) * 2003-02-06 2007-07-03 Equistar Chemicals, Lp High density polyethylene and insulation compositions for wire and cable
US7335694B2 (en) * 2002-02-14 2008-02-26 Sumitomo Chemical Company, Limited Polypropylene resin composition
US7744972B2 (en) * 2003-12-04 2010-06-29 Dow Global Technologies Inc. Stabilized polyethylene material

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5931929B2 (en) * 1979-12-04 1984-08-06 住友化学工業株式会社 Ethylene polymer water pipe
SU1072420A1 (en) 1982-04-23 1996-11-20 Новосибирский институт органической химии СО АН СССР Bis-[(3,5-di-tert-butyl-4-hydroxyphenyl)-alkyl]-sulfides as thermostabilizing agents of polyethylene
US4532165A (en) * 1983-05-09 1985-07-30 Mitsui Petrochemical Industries Ltd. Poly-1-butene resin composition
JPS6456747A (en) 1987-08-27 1989-03-03 Mitsubishi Petrochemical Co Pipe for plumbing system
US4812500A (en) * 1987-09-30 1989-03-14 Shell Oil Company Polyolefin compositions for water pipes and for wire and cable coatings
JP2580252B2 (en) 1988-05-16 1997-02-12 三菱化学株式会社 Hot and cold water transfer pipe
DE19515678B4 (en) 1995-04-28 2007-12-27 Basell Polyolefine Gmbh Polyethylene tube with improved mechanical properties
US5767034A (en) 1996-05-31 1998-06-16 Intevep, S.A. Olefin polymerization catalyst with additive comprising aluminum-silicon composition, calixarene derivatives or cyclodextrin derivatives
US6521681B1 (en) * 1996-07-05 2003-02-18 Ciba Specialty Chemicals Corporation Phenol-free stabilization of polyolefin fibres
JPH1056747A (en) 1996-08-08 1998-02-24 Sanyo Electric Co Ltd Wedge for compressor motor
US5858246A (en) * 1997-01-14 1999-01-12 Fountainhead Technologies, Inc. Method of water purification with oxides of chlorine
TW557452B (en) * 1997-12-15 2003-10-11 Borealis As A composition for an electric cable
JP4008097B2 (en) 1998-04-09 2007-11-14 日本ポリオレフィン株式会社 Polyethylene resin composition for water pipes, water pipes and pipe fittings
RU2156003C1 (en) * 1999-12-28 2000-09-10 Башкирский государственный университет (БашГУ) Electroinsulating composition
JP2003012946A (en) 2001-04-27 2003-01-15 Api Corporation Resin material deterioration inhibitor, chlorine-resistant aqueous resin composition, and deterioration suppression method
EP1266933A1 (en) 2001-06-14 2002-12-18 SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) Polyethylene blends
US7086421B2 (en) * 2002-07-23 2006-08-08 Noveon Ip Holdings Corp. Crosslinked polyethylene pipe having a high density polyethylene liner
ES2609456T3 (en) 2002-12-18 2017-04-20 Borealis Technology Oy Method for the preparation of an olefin polymerization catalyst support and an olefin polymerization catalyst
DE10316845A1 (en) 2003-04-11 2004-11-11 Rehau Ag + Co. polyolefin pipe
US7008543B2 (en) * 2003-04-14 2006-03-07 Contra Costa Water District Use of chlorine dioxide and ozone for control of disinfection by-products in water supplies
JP2004315715A (en) * 2003-04-18 2004-11-11 Toyo Ink Mfg Co Ltd Colored resin composition resistant to chlorine-containing water and water pipe
US20060264540A1 (en) * 2005-05-19 2006-11-23 Gelbin Michael E Stabilizer blend for improved chlorine resistance
EP2199327A1 (en) 2008-12-22 2010-06-23 Borealis AG Polyolefin composition for water pipes with increased resistance to chlorine dioxide

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3370036A (en) * 1962-07-02 1968-02-20 Phillips Petroleum Co Stabilization of polymers with uv stabilizers and antioxidants
GB1087403A (en) * 1963-10-28 1967-10-18 Raychem Corp Improved cross-linked polymer compositions and a process for their manufacture
DE1947071A1 (en) * 1968-09-24 1970-09-17 Monsanto Chemicals Electric cables
US4131599A (en) * 1975-05-28 1978-12-26 Sankyo Company, Limited Stabilization of poly(mono-olefins)
US4221699A (en) * 1977-06-14 1980-09-09 Societe Anonyme De Telecommunications Production of extruded polyolefin products
CA1120630A (en) * 1977-10-12 1982-03-23 Olaf E. Larsen Pipe extrusion polymeric blend
JPS5859025A (en) * 1981-09-25 1983-04-07 Tokyo Electric Power Co Inc:The Manufacture of joined section of cable insulated with crosslinked polyethylene
JPH02153955A (en) * 1988-07-07 1990-06-13 Nippon Unicar Co Ltd Polyethylene composition for water pipe
US5266616A (en) * 1991-07-12 1993-11-30 Phillips Petroleum Company Polyolefin resin formulation using organic pigments
US6541547B1 (en) * 1995-09-15 2003-04-01 Ciba Specialty Chemicals Corporation Process for stabilization of polyolefins in permanent contact with extracting media
JPH11147976A (en) * 1997-11-17 1999-06-02 Toyo Ink Mfg Co Ltd Chlorine-resistant aqueous colored resin composition and water pipe
US20030158306A1 (en) * 1998-10-21 2003-08-21 Battiste David R. Phosphite additives in polyolefins
US6680351B1 (en) * 1999-07-20 2004-01-20 Phillips Petroleum Company Phosphite additives in polyolefins
US6538056B1 (en) * 2000-10-10 2003-03-25 Clariant International Ltd. Polyolefin articles with long-term elevated temperature stability
US7335694B2 (en) * 2002-02-14 2008-02-26 Sumitomo Chemical Company, Limited Polypropylene resin composition
US7238765B2 (en) * 2003-02-06 2007-07-03 Equistar Chemicals, Lp High density polyethylene and insulation compositions for wire and cable
US7744972B2 (en) * 2003-12-04 2010-06-29 Dow Global Technologies Inc. Stabilized polyethylene material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DE1947071A, 09-1970, DERWENT Ab. *
JP02153955A, 06-1990, English Ab. *
JP11147976 A, 06-1999, Machine translation. *
JP58059025A, 04-1983, DERWENT Ab. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140004287A1 (en) * 2011-03-14 2014-01-02 Dow Globel Technologies LLC Ethylene-based compositions
US20150299903A1 (en) * 2014-04-18 2015-10-22 Asahi Kasei Chemicals Corporation Polyethylene Powder for Fiber, Fiber, and Article
US10597796B2 (en) * 2014-04-18 2020-03-24 Asahi Kasei Chemicals Corporation Polyethylene powder for fiber, fiber, and article

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