WO2020003048A1 - Stabilisateurs de polyoléfines à fragmentation réduite - Google Patents

Stabilisateurs de polyoléfines à fragmentation réduite Download PDF

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Publication number
WO2020003048A1
WO2020003048A1 PCT/IB2019/055037 IB2019055037W WO2020003048A1 WO 2020003048 A1 WO2020003048 A1 WO 2020003048A1 IB 2019055037 W IB2019055037 W IB 2019055037W WO 2020003048 A1 WO2020003048 A1 WO 2020003048A1
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WO
WIPO (PCT)
Prior art keywords
stabilizer
light
hindered amine
polyolefine
group
Prior art date
Application number
PCT/IB2019/055037
Other languages
English (en)
Inventor
Klaus Keck
Original Assignee
Songwon Industrial Co., Ltd.
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 Songwon Industrial Co., Ltd. filed Critical Songwon Industrial Co., Ltd.
Publication of WO2020003048A1 publication Critical patent/WO2020003048A1/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
    • C08K5/34—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
    • 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
    • C08K5/17—Amines; Quaternary ammonium 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the present invention relates to a polyolefine composition containing stabilizers and articles made using such polyolefine compositions, such as pipes, packaging, especially food- packaging articles or the like.
  • antioxidants can prevent or at least reduce these effects.
  • these stabilizers usually have a far lower molecular weight than the polyolefine, a further important issue as regards the presence of antioxidants in polyolefine compositions is the aim to reduce migration of antioxidants or degradation products received therefrom into media e.g. into water in a pipe made of such a polyolefine composition or into food from a packaging article made of such a polyolefine composition. This is particularly important in case of a pipe transporting drinking water. Due to the permanent contact to the inner pipe surface, compounds can migrate from the pipe material into the water. The admissible amounts of compounds within the drinking water are fixed by legal requirements and even stricter requirements are to be expected in Europe or other countries. This not only goes for the stabilizers as such but to some extent even more for products which arise out of the fragmentation of such stabilizers.
  • a stabilizer composition comprising a hindered amine (light) stabilizer and a processing stabilizer which essentially does not contain a hydrolizable phosphite compound having 2-4-substituted phenol moiety, in polyolefines for reducing the amount of pollutants resulting from the fragmentation of the stabilizer composition.
  • the present invention also relates to a method for reducing the amount of pollutants resulting from the fragmentation of a stabilizer composition by adding a stabilizer composition, comprising a hindered amine (light) stabilizer and a processing stabilizer which essentially does not contain a hydrolizable phosphite compound having 2-4-substituted phenol moiety, to a polyolefine.
  • polyolefine especially means and/or includes all substrates as defined in US 2015/0090671 Al, US 2014/0296398 Al, WO 2006/119935 Al and/or US 2005/0148700 Al.
  • Hindered amine (light) stabilizer
  • the stabilizer composition comprises a hindered amine (light) stabilizer.
  • the role of that hindered amine (light) stabilizer is to stabilize the polyolefine against degradation due to light (including UV light) and/or radicals and/or oxygen.
  • the term“hindered amine (light) stabilizer” (in the following referred to as HA(L)S) especially means and includes amines with bulky groups in a-position to the amine.
  • HA(L)S compounds which comprise the following moiety:
  • the stabilizer composition comprises a HA(L)S compound which comprises 2 to 30, preferably 5 to 25 of these moieties.
  • HA(L)S compounds which comprise the following moiety
  • the stabilizer composition comprises a HA(L)S compound which comprises 2 to 30, preferably 5 to 25 of these moieties
  • the stabilizer composition comprises a HA(L)S compound which comprises a triazine. This has been found to be especially advantageous in food packaging applications.
  • the stabilizer composition comprises a HA(L)S compound with a molecular weight of >1000 to ⁇ 4000 Da, especially >1500 to ⁇ 3000 Da.
  • HA(L)S compounds are compounds known under the name Chimassorb 119 or Sabostab UV 119 (CAS 106990-43-6), Chimassorb 2020 or Sabostab UV 40 (CAS 192268-42-7), Sabostab UV 62, Hostavin N30, ADK Stab LA 52 and ADK Stab LA 57.
  • the stabilizer composition consists essentially out of one or more HA(L)S compounds, preferably out of HA(L)S compounds described as especially preferred before.
  • processing stabilizer especially means and/or includes a compound which-protects the polyolefine in the molten state from auto-oxidation.
  • Processing stabilizers can, depending on the application and/or preferred embodiment and/or their chemical nature either act alone or as synergist to the hindered amine (light) stabilizer. It should be noted that the processing stabilizer itself is not a hindered amine (light) stabilizer according to a preferred embodiment of the present invention.
  • phosphite means and/or relates to the major chemical class of processing stabilizers utilized in polyolefines.
  • An overview over typical molecules is given on page 109 to 112 of the Plastics Additive Handbook (Hanser Publishers, 5 th Edition (2001)). It can be noted that the preferred subclass within phosphites comprised 2-4-substituted phenol moieties.
  • the principle chemistry and advantages of this chemical class are outlined on page 14 of the same reference. Also noted (on the same page) is the principle weakness of this chemical class; being its sensitivity to hydrolysis.
  • hydrolizable phosphite especially means and/or relates to the effect described on the bottom of page 45 and on the bottom of page 47 (of the above publication). While there is a difference in the rate of hydrolysis, yielding at different rates fragmentation products, it is generally accepted that all commonly used phosphites do hydrolysis.
  • the processing stabilizer comprises, preferably consists essentially of a compound selected out of the group comprising phosphites, phosphonites, N-hydroxylamines, natural antioxidants, especially selected from the group comprising curcumin, quercetin, naringenin, beta-carotin, resveratrol, Vitamin E and derivatives of all these compounds, cyclic pentaerythritole diphosphite esters, partially unsaturated hydrocarbons or mixtures thereof.
  • the processing stabilizer comprises, preferably consists essentially of a compound selected out of the group comprising phosphites, phosphonites, natural antioxidants, especially selected from the group comprising curcumin, quercetin, naringenin, beta-carotin, resveratrol, Vitamin E and derivatives of all these compounds, cyclic pentaerythritole diphosphite esters, partially unsaturated
  • hydrocarbons or mixtures thereof are hydrocarbons or mixtures thereof.
  • the processing stabilizer and/or the stabilizer composition does not contain N-hydroxylamines.
  • the processing stabilizer composition does not comprise an antioxidant according to the following structure:
  • R 8 , R 9 ; R 10 , R 11 , and R 12 independently are H, or non-substituted aliphatic or aromatic hydrocarbyl radicals which may comprise heteroatoms.
  • the processing stabilizer composition does not comprise vitamin E.
  • the stabilizer composition further comprises an acid scavenger. Consequently the present invention also relates to the use of a stabilizer composition as described above together with an acid scavenger.
  • acid scavenger especially means and/or includes a compound which neutralizes acidity which may originate from the polymerisation catalyst of the polyolefine synthesis; usually this will be mainly Ziegler/Nata catalysts. It is understood, that not every catalyst used for polyolefine synthesis requires an acid scavenger.
  • the acid scavenger comprises, preferably consists essentially of a metal oxide, metal hydroxide, metal organic salt and/or metal carbonate.
  • the acid scavenger comprises a layered double hydroxide compound.
  • Layered double hydroxides (LDHs) in the sense of the present invention are defined as layered materials with positively charged layers and charge balancing anions located in the interlayer region. This is unusual in solid state chemistry as many more families of materials have negatively charged layers and cations in the interlayer spaces (e.g. kaolinite,
  • LDHs layered double hydroxides
  • M n is a divalent metal ion, preferably Mg 2+ , Ca 2+ , Mn 2+ , Fe 2+ , Zn 2+ , Cu 2+ , Ni 2+ and Co 2+ ;
  • M ni is a trivalent metal ion, preferably Al 3+ , Cr 3+ , Fe 3+ , Ga ⁇ 3+ >and Mn 3+ ,
  • a n is an anion, preferably Cl , C03 2 , N03 , Br , S04 2 and alkyl sulfonates, alky aryl sulfonates, organic carboxylates, organic phosphates or mixtures thereof, more preferably Cl , C03 2 , N03 , Br , S04 2 or mixtures thereof
  • y is number of water molecules needed to stabilize the crystal structure, usually y is within the range of 0.25 to 4, preferably 0.5 to 4, more preferably 0.5 to 1.0; x is usually within the range of 0.1 to 0.5, preferably within the range of 0.10 to 0.38, more preferably within the range of 0.10 to 0.33;
  • LDHs Layered double hydroxides
  • n is an alkyl sulfonate
  • the alkyl group is usually a Cl to C20 alkyl group.
  • n is an alky aryl sulfonate the alky aryl group is a C6 to C20 alky aryl group.
  • n is an organic carboxylate
  • the organic group attached to the carboxylate group(s) usually contains 1 to 20 carbon atoms and up to 5 heteroatoms, preferably, if present, the heteroatoms are selected from N, O, P and S.
  • the organic carboxylate comprises 1 to 2 carboxylate groups, preferably 1 carboxylate group.
  • organic group attached to the carboxylate group(s) denotes that the carboxylate groups are not part of the organic group.
  • the oxygen and carbon atoms present in the carboxylate group do not count for the organic group.
  • the organic group is methyl.
  • n is an organic phosphate
  • the organic group(s) attached to the phosphate group(s) independently usually contains 1 to 20 carbon atoms and up to 5 heteroatoms, preferably, if present, the heteroatoms are selected from N, O, P and S.
  • the organic phosphate comprises one phosphate group and one organic group.
  • organic group(s) attached to the phosphate group(s) denotes that the phosphate groups are not part of the organic group(s). Thus, the oxygen and phosphor atoms present in the phosphate group do not count for the organic group. Thus, for example in case of methyl phosphate the organic group is methyl.
  • LDHs layered double hydroxides
  • M n is selected from M PI is Al 3+ ;
  • a n is an anion selected from Cl , C03 2 and N03
  • y is within the range of 0.25 to 4, preferably within the range of 0.5 to 1.0
  • x is within the range of 0.10 to 0.38, preferably within the range of 0.10 to 0.33,
  • the layered double hydroxides (LDHs) is selected from
  • hydrotalcite Especially preferred are hydrotalcite, hydrocalumite, metal fatty acids, zink oxide and calcium carbonate.
  • the present invention especially relates to a polyolefine composition, comprising a polyolefine, a hindered amine (light) stabilizer and a processing stabilizer as described above and a layered double hydroxide.
  • the present invention furthermore relates to a product making use of the inventive use.
  • the product comprises a product selected from the group comprising
  • the present invention especially relates to rigid and flexible food packaging as well as further food appliances.
  • the migration tests were performed using the following standard procedure.
  • the polymer was synthesized with a Ziegler/Natta catalyst.
  • the compounding of the polyolefine took place using a Toshiba TEM 37BS twin screw extruder with a temperature profile from l90°C to 2l5°C under nitrogen. In order to match or at least simulate the processing conditions of industrial equipment, this extrusion was repeated five times.
  • the migration tests were performed using the following standard procedure.
  • melt flow index is a very crude (but simple and practical) rheological measurement of the flow behavior of polymer melts at a given temperature and for one single, given shear rate. It is proportional to the molecular weight of the polymer.
  • An increase in melt flow index corresponds to a decrease in molecular weight due to chain scission, while a decrease in melt flow index corresponds to an increase in molecular weight due to crosslinking reactions.
  • the yellowness index is a measure of the discoloration of a (plastic) material with specific emphasis on the yellowing (in contrast to whiteness index and total color change). It is calculated according to the following equation
  • YI measurement were carried out in accordance with ISO E 313 on a Greytag Macbeth Spectro Eye. For productivity reasons, YI is measured on polyethylene granules rather than on moulded plaques; although the latter yield more precise results.

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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

L'invention concerne une composition de polyoléfine ayant un stabilisateur d'amine encombrée (léger) et un stabilisateur de traitement de sorte que moins de polluants émergent de la polyoléfine.
PCT/IB2019/055037 2018-06-25 2019-06-17 Stabilisateurs de polyoléfines à fragmentation réduite WO2020003048A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018115226.4 2018-06-25
DE102018115226 2018-06-25

Publications (1)

Publication Number Publication Date
WO2020003048A1 true WO2020003048A1 (fr) 2020-01-02

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100222471A1 (en) * 2006-02-01 2010-09-02 Cesare Lorenzetti Stabilizer Composition for Polymers
WO2014020170A1 (fr) * 2012-08-02 2014-02-06 Addivant Switzerland Gmbh Compositions de phosphite
US20160280863A1 (en) * 2015-03-25 2016-09-29 Zimmer, Inc. Melt-stabilized ultra high molecular weight antioxidant
WO2017023755A1 (fr) * 2015-07-31 2017-02-09 Cytec Industries Inc. Compositions encapsulées de stabilisant
US20170058151A1 (en) * 2014-04-29 2017-03-02 Basf Se Multi-layered film and the use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100222471A1 (en) * 2006-02-01 2010-09-02 Cesare Lorenzetti Stabilizer Composition for Polymers
WO2014020170A1 (fr) * 2012-08-02 2014-02-06 Addivant Switzerland Gmbh Compositions de phosphite
US20170058151A1 (en) * 2014-04-29 2017-03-02 Basf Se Multi-layered film and the use thereof
US20160280863A1 (en) * 2015-03-25 2016-09-29 Zimmer, Inc. Melt-stabilized ultra high molecular weight antioxidant
WO2017023755A1 (fr) * 2015-07-31 2017-02-09 Cytec Industries Inc. Compositions encapsulées de stabilisant

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