EP3853300A1 - Use of a low molecular weight triazine based compound as thermal / light stabilizer in polymers - Google Patents
Use of a low molecular weight triazine based compound as thermal / light stabilizer in polymersInfo
- Publication number
- EP3853300A1 EP3853300A1 EP19783214.0A EP19783214A EP3853300A1 EP 3853300 A1 EP3853300 A1 EP 3853300A1 EP 19783214 A EP19783214 A EP 19783214A EP 3853300 A1 EP3853300 A1 EP 3853300A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substituted
- based compound
- triazine based
- alkyl
- use according
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 13
- 239000003017 thermal stabilizer Substances 0.000 title claims abstract description 13
- 229920000642 polymer Polymers 0.000 title claims description 39
- -1 mono-substituted nitrogen atoms Chemical group 0.000 claims abstract description 40
- 229920000098 polyolefin Polymers 0.000 claims abstract description 31
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical group 0.000 claims abstract description 9
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 abstract description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 15
- 239000003381 stabilizer Substances 0.000 description 13
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 9
- 235000006708 antioxidants Nutrition 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229940032094 squalane Drugs 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- RUYGGEDMXNDORB-UHFFFAOYSA-N 4-(2,2,6,6-tetramethylpiperidin-4-yl)-1H-1,3,5-triazine-2,4,6-triamine Chemical compound CC1(NC(CC(C1)C1(NC(=NC(=N1)N)N)N)(C)C)C RUYGGEDMXNDORB-UHFFFAOYSA-N 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical class 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LANFMNFQTUQWEF-UHFFFAOYSA-N 4-methylpent-1-ene Chemical compound C[C](C)CC=C LANFMNFQTUQWEF-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007609 Zn—S Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
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- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—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
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
Definitions
- the present invention relates to the use of low molecular weight triazine based compounds for increasing the resistance of polymers against degradation caused by heat and light; to polymer compositions with increased resistance to heat and light and to the use of such polymer compositions for producing articles.
- Such aging processes are normally based on oxidation reactions which are caused by heat, light, mechanical stress, catalysis or reactions with impurities.
- the aging of polymeric materials can occur during their production, during processing into shaped parts by moulding, extrusion, etc. and/or during use of the shaped parts.
- stabilizers such as antioxidants, light stabilizers and heat / thermal stabilizers can prevent or at least reduce these effects by adding them to the polymers to protect them during processing and to achieve the desired end-use properties.
- Antioxidants interrupt the degradation process in different ways, depending on their structure.
- the two major classifications are chain terminating primary antioxidants and hydroperoxide decomposing secondary antioxidants.
- Primary antioxidants react rapidly with peroxy radicals and are therefore called “radical scavengers”.
- the majority of primary antioxidants for polyolefins are sterically hindered phenols.
- Triazine based Mannich compounds have also shown to protect polyolefins against oxidative degradation and degradation caused by UV radiation (WO 2013/041592 A1 ). In contrast, phenolic compounds do not function well as light stabilizers.
- the heat stabilizing effect of a compound is strongly influenced by the temperature the polymer is exposed to and the protection mechanism.
- the polymer degradation at high temperatures is mainly due to the oxidation of the polymer itself, while at low temperatures the secondary oxidation of (smaller) oxidation products such as aldehydes is more important.
- Hindered amine light stabilizers are chemical compounds containing an amine functional group that are used as stabilizers in plastics and polymers. HALS do not absorb UV radiation, but act to inhibit degradation of the polymer by continuously and cyclically removing free radicals that are produced by photo-oxidation of the polymer. Broadly, HALS react with the initial polymer peroxy radical (ROO) and alkyl polymer radicals (R ⁇ ) formed by the reaction of the polymer and oxygen, preventing further radical oxidation. By these reactions HALS are oxidised to their corresponding aminoxyl radicals (R 2 NO c.f. TEMPO), however they are able to return to their initial amine form via a series of additional radical reactions. HALS's high efficiency and longevity are due to this cyclic process wherein the HALS are regenerated rather than consumed during the stabilization process.
- ROO initial polymer peroxy radical
- R ⁇ alkyl polymer radicals
- HALS are capable of preventing the oxidation of aldehydes, but do not influence the oxidation rate of polymers (hydrocarbons). Thus, HALS are known as good heat stabilizers at low temperatures (P. Gijsman, Polymer Degradation and Stability, 1994, 43: 171 -176).
- HALS Compared to the phenolic antioxidants the main benefit of HALS when used as thermal stabilizers are 1 ) high efficiency up to certain temperatures; 2) no or low discoloring. In particular the low discoloring provides the unique opportunity of HALS for some applications, such as low (no) gas fading fibre, or medical devices where specific sterilization technique are used (e.g. gamma radiation).
- the key limitation is the application temperature of HALS stabilized compounds. In most cases, HALS has an effective thermal stabilizing effect upto a temperature of about Q ' ⁇ . Beyond that temperature the efficiency drops significantly and conventional HALS are not suitable for applications above I dO ' ⁇ anymore.
- the present invention relates to the use of a triazine based compound of the general formula (I) wherein
- R 1 is hydrogen, halogen, substituted or non-substituted hydroxy, substituted or non- substituted amino, substituted or non-substituted C5-C20 aryl, substituted or non-substituted, linear or branched Ci-Ci 2 -alkyl, substituted and non-substituted, linear or branched C2-C12- alkenyl, wherein Ci-Ci 2 -alkyl and C 2 -Ci 2 -alkenyl can be interrupted by one or more atoms or groups selected from oxygen atoms, substituted or mono-substituted nitrogen atoms, double bonds, siloxan groups and/or by one or more groups of the type -C(0)0-, -OC(O)-, -C(O)-, - C(0)NH-,-NHC(0)0-, -0C(0)NH-, -NHC(0)NH- and/or -00(0)0-, whereby the atoms and groups selected from oxygen atom
- R 2 and R 3 are substituted and/or non-substituted C 3 -Cio-cycloalkyl, which comprises at least one nitrogen atom in the ring structure; as thermal stabilizer and/or light stabilizer in polyolefins at temperatures at or above
- a low molecular weight compound in particular with a molecular weight ⁇ 2000, preferably ⁇ 1800, more preferably ⁇ 1500, most preferably ⁇ 1200, is provided that can be used as light stabilizer, but in particular as thermal and/or light stabilizer in thermoplastic polymers at temperatures above I dO ' ⁇ .
- the triazine based compound show an improved stability effect at temperatures above 150 ' ⁇ when compared to conventionally used stabilizers such as 1 ,3,5-T ris(3’,5’-di-tert. butyl-4’-hydroxybenzyl)-isocyanurate (Irganox 31 14).
- Thermal and light stabilizing effects in particular at temperatures above I dO ' ⁇ , can also be described as overlapping effects.
- the HALS of the present invention may also be described as having light stabilizing effects at different temperatures, in particular above I dO ' ⁇ .
- the HALS compounds of the present invention protect the polyolefin against thermo oxidative degradation.
- the triazine based compound used in this invention have been described previously.
- DE 2319816 A1 discloses a family of triazine based HALS compounds used a light stabilizers in polymers. However, the use of such a triazine based compound as thermal stabilizer in polyolefins at elevated temperatures above I dO' ⁇ is not described.
- the triazine based compound of the invention has been used either as reactive substances, to create the high molecular weight HALS or with other polymers such as polyamid to form stabilized compositions. So far, no direct use of the triazine based molecules as thermal stabilizer in polyolefins is described.
- R 1 is hydrogen, halogen, substituted or non-substituted hydroxy, substituted or non-substituted amino, substituted or non-substituted C 1 -C 5 alkyl, substituted or non-substituted C 6 -Ci 2 aryl; and the moieties R 2 and R 3 are substituted and/or non-substituted C3-C 7 -cycloalkyl, which comprises at least one nitrogen atom in the ring structure.
- the moiety R 1 is from a group consisting of halogen, - OCH 3 , -OC 2 H 5 , substituted or non-substituted amino, methyl and phenyl.
- the moiety R 1 is halogen, such as chlorine, fluorine or bromine, in particular chlorine, or a primary amino group.
- the moieties R 2 and R 3 are substituted and/or non-substituted C 3 -C 7 - cycloalkyl, which comprises one or two nitrogen atoms in the ring structure.
- the triazine based compound of the general formula (I) comprises the following structure (II)
- R 4 and R 5 are selected independently from each other from substituted or non- substituted, linear or branched CrCis-alkyl, preferably substituted or non-substituted, linear or branched Ci-Cio-alkyl, and
- - n is 0 to 8, preferably 2-4.
- triazine based compound of the general formula (I) comprises the following structure (III)
- R 4a d and R 5a d are selected from substituted or non-substituted, linear or branched Cr C 5 -alkyl, preferably substituted or non-substituted, linear or branched C1-C3 alkyl.
- triazine based compound of the general formula (I) comprises the following structure (IV)
- R 1 has one the above meanings
- substituted in connection to aryl, alkyl, alkenyl and cycloalkyl relates to the substitution of one or more atoms, usually H-atoms, by one or more of the following substituents: halogen, hydroxy, protected hydroxy, oxo, protected oxo, C 3 -C 7 -cycloalkyl, phenyl, naphtyl, amino, protected amino, primary or secondary amino, heterocyclic ring, imidazolyl, indolyl, pyrrolidinyl, Ci-Ci 2 -alkoxy, Ci-Ci 2 -acyl, CrCi 2 -acyloxy, nitro, carboxy, carbamoyl, carboxamid, N-(Ci-Ci 2 -alkyl)carboxamid, N,N-Di(Ci-Ci 2 -alkyl)carboxamid, cyano, methylsulfonylamino, thiol
- substituted in connection to hydroxy and amino relates to the substitution of at least one H atom by one or in case of amino one or two of one of the substituents mentioned above, in particular substituted and non-substituted, linear or branched Ci-Ci 2 -alkyl, substituted and non-substituted C 3 -C 7 -cycloalkyl and substituted and non-substituted, linear or branched C 2 - Ci 2 -alkenyl.
- the hydroxy group can be present as an ether group.
- Amino group can be present as a primary or secondary amine.
- the term “suitalkyl“ relates to moieties like methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s- butyl, t-butyl, amyl, t-amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and alike.
- Preferred alkyl groups are methyl, ethyl, isobutyl, s-butyl, t-butyl und isopropyl.
- oxo relates to a carbon atom, which is connected with an oxygen atom via a double bond whereby a keto or an aldehyde group is formed.
- protected oxo relates to a carbon atom, which is substituted by two alkoxy groups or is connected twice with a substituted diol forming a non-cyclic or cyclic ketal group.
- the term relates to moieties like methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t- butoxy and alike.
- a preferred alkoxy group is methoxy.
- Thus comprises groups like cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl und cycloheptyl.
- the preparation of the triazine based compound suitable as stabilizer can be done for example by reacting cyanuric chloride with 4-Amino-2,2,6,6-tetramethylpiperidine 6-Chloro-A/ 2 ,A/ 4 - bis(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4-diamin (C 21 H 38 CIN 7, 1 ), which may react further to A ⁇ ,A/ 4 -(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4,6-triamin (2).
- the triazine based compound is used as thermal stabilizer and/or light stabilizer in polyolefins in a temperature range between 150‘O and 250 °C, preferably between I dO' ⁇ and 200‘O, more preferably between I QO' ⁇ and 180°C.
- the triazine based compound is added to the thermoplastic polymer in a concentration between 200 and 5000 ppm, preferably between 500 and 3000 ppm, more preferably between 1000 and 2000 ppm.
- concentration range is between 350 - 2500 ppm.
- polyolefins to be stabilized are for example:
- polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut- 1 -ene, poly-4-methylpent-1 -ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example of cyclopentene or norbornene; furthermore polyethylene (which optionally can be crosslinked); for example, high density polyethylene (HDPE), polyethylene of high density and high molar mass (HDPE-HMW), polyethylene of high density and ultrahigh molar mass (HDPE-UHMW), medium density polyethylene (HMDPE), low density polyethylene (LOPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
- HDPE high density polyethylene
- HDPE-HMW polyethylene of high density and high molar mass
- HDPE-UHMW polyethylene of high density and ultrahigh molar mass
- HMDPE medium density polyethylene
- LOPE
- - Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-but-1 -ene copolymers, propylene-isobutylene copolymers, ethylene-but-1 -ene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene- octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene-acrylic acid copolymers and their salts
- Polyolefins i.e. polymers of monoolefins exemplified in the preceding paragraphs, in particular polyethylene and polypropylene, can be prepared by various, and especially by the following, methods:
- metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coordinated.
- These metal complexes may be in the free form or fixed on substrates, for example on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
- These catalysts may be soluble or insoluble in the polymerization medium.
- the catalysts can be active as such in the polymerization or further activators may be used, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements of groups la, I la and/or Ilia of the Periodic Table.
- the activators may be modified, for example, with further ester, ether, amine or silyl ether groups.
- These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler-Natta, TNZ (DuPont), metallocene or single site catalysts (SSC).
- the polyolefin is selected from polyethylen, polypropylen, high pressure polyethylene or copolymers thereof.
- halogenated polyolefins in particular chlorinated polyeolefins, such as PVC
- chlorinated polyeolefins such as PVC
- hydrogen halides such as HCI
- additional compounds are added to the halogenated polyolefins which interact with the released hydrogen halides.
- organozinc compounds in particular organozinc compounds containing a Zn-0 or a Zn-S bond, such as Zn-stearate, are used for such purposes.
- non-halogenated polyolefins are preferably used.
- the polyolefins applied in the present case are free of any additional organometallic compounds that is not a catalyst or activator, in particular free of any organozinc compound.
- the present invention consequently, relates to a method of stabilizing a polyolefin against thermal and/or light degradation by incorporating an amount of a triazine based compound as defined above.
- the present invention also relates to a polymer composition
- a polymer composition comprising a polyolefin and a triazine based compound as defined above.
- the triazine based compound may be present in the polymer composition in a concentration between 200 and 5000 ppm, preferably between 500 and 3000 ppm, more preferably between 1000 and 2000 ppm. The most preferred concentration range is between 350 - 2500 ppm.
- the triazine based compounds of the formula (I) or mixtures therefrom of the present invention may be combined with a variety of additives conventionally employed in the antioxidant and/or UV stabilizing art, such as (further) anti oxidants, (further) UV absorbers and stabilizers, metal deactivators, antistatics, phosphites and phosphonites, hydroxylamines, nitrones, thiosynergists, co-stabilizers, nucleating agents, fillers and reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, level agents, optical brighteners, flameproofing agents, anti-static agents and blowing agents.
- additives are described in the "Plastics Additives Handbook".
- triazine based compounds useful as stabilizer according to the present invention optionally in combination with a further stabilizer or additive may be added to the polyolefin to be stabilized individually or mixed with one another. If desired, the individual components of such a stabilizer mixture can be mixed with one another in the melt (melt blending) before incorporation into the polyolefin to be stabilized.
- the incorporation of the triazine based compound of the invention and optional further components into the polyolefin is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
- the triazine based compounds of the invention and optional further additives may be incorporated, for example, before or after moulding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc), e.g. as a dry mixture or powder or as solution or dispersion or suspension or melt.
- the incorporation can be carried out in any heatable container equipped with a stirrer, e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
- a stirrer e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
- the incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.
- the addition of the additive or additive blend to the polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
- the process is preferably carried out in an extruder by introducing the additive during processing.
- Particularly preferred processing machines are single-screw extruders, contrarotating and corotating twinscrew extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied. Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffextrusion, Vol. 1 Kunststoffn, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol.
- the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters.
- the rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), very particularly preferably 25 - 300 rpm.
- the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
- the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts. If a plurality of components is added, these can be premixed or added individually.
- the triazine based compounds of the invention and optional further additives can also be added to the polymer in the form of a masterbatch ("concentrate") which contains the components in a concentration of, for example, about 1 % to about 40% and preferably 2 % to about 20 % by weight incorporated in a polymer.
- concentration a masterbatch
- the polymer need not be necessarily of identical structure than the polymer where the additives are added finally.
- the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
- Incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices.
- a further possibility for incorporating the additives of the invention into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking. In this context the additive of the invention can be added as it is or else in encapsulated form (for example in waxes, oils or polymers).
- polymer compositions in particular the polyolefin compositions, containing the triazine based compounds of the invention described herein can be used for the production of mouldings, rotomoulded articles, injection moulded articles, blow moulded articles, pipes, films, tapes, mono-filaments, fibers, nonwovens, profiles, adhesives or putties, surface coatings and the like.
- the invention is explained in more detail in the following examples.
- Example 1 6-Chloro-A ⁇ ,A/ 4 -bis(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4-diamin (HALS 2)
- Cyanuric chloride reacts with 4-Amino-2,2,6,6-tetramethylpiperidine to 6-Chloro-A ⁇ ,A/ 4 - bis(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4-diamin (C 21 H 38 CIN 7 ), called HALS2, as shown in
- Example 2 A ⁇ ,A/ 4 -(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4,6-triamin (HALS 4)
- HALS2 reacts with ammonia to A ⁇ ,A/ 4 -(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4,6- triamin , called HALS4, as shown
- the oxidative induction time is the measured time in which the oxidation of a sample is inhibited by an existing antioxidant stabilizer system.
- the OIT is measured while the sample is kept constant at a certain temperature under an oxygen stream.
- the measurement is performed in a differential scanning calorimeter (DSC).
- DSC differential scanning calorimeter
- the sample and the reference are heated under constant nitrogen atmosphere to a specific temperature. When this temperature is reached, the gas flow switches to oxygen at the same flow rate. Until the oxidative degradation starts, the material is held at a constant temperature.
- the OIT is represented on a thermal curve. It is the time span between the start of the oxygen and the onset of the oxidative degradation reaction. The onset is indicated by a sudden change in heat flow.
- the OIT measurements are carried out according to ISO 1 1357-6 on a Mettler Toledo DSC822e. The measurements are done with open pans.
- Sample preparation 0.2 wt% active group equivalent are mixed into Squalane (SQ).
- Squalane is used as matrix material due to its chemical similarity to PP and the easier handling.
- the structure is shown in Scheme 3. The stabilizer and SQ are first mixed in an ultrasonic bath and then with stirring to afford a homogenous suspensions.
- the measurement is stopped when the degradation starts.
- the degradation is indicated with a sudden change in the heat flow curve indicating an exothermal process.
- the OIT-curves for HALS2 and HALS4 at 160 °C are shown in Table 1 .
- Tinuvin 770 Bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate) and Irganox 31 14 (1 ,3,5-T ris(3’,5’- di-tert. butyl-4’-hydroxybenzyl)-isocyanurate) are used as comparative examples CE1 and CE2, respectively.
- Table 1 lists the OIT of Inventive Examples (lEs) and Comparative Examples (CEs). Surprisingly it was found that by proper design the molecules, the IE do not work only at low T (like I Od' ⁇ ), but also works at higher T (like 160°C), which is typically not the case of HALS and rather on the same level as phenolic antioxidants.
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Abstract
The present invention relates to the use of a triazine based compound of the general formula (I), wherein R1 is hydrogen, halogen, substituted or non-substituted hydroxy, substituted or non- substituted aminosubstituted or non-substituted C5-C20 aryl, substituted or non-substituted, linear or branched C1-C12-Alkyl, substituted and non-substituted, linear or branched C2-C12-alkenyl, wherein Ci-Ci2-alkyl and C2-C12-alkenyl can be interrupted by one or more atoms or groups selected from oxygen atoms, substituted or mono-substituted nitrogen atoms, double bonds, siloxan groups and/or by one or more groups of the type -C(O)O-, -OC(O)-, -C(O)-, - C(O)NH-,-NHC(O)O-, -OC(O)NH-, -NHC(O)NH- and/or -OC(O)O-, whereby the atoms and groups selected from oxygen atoms, -OC(O)-, -C(O)-, -NHC(O)O-, -NHC(O)NH- or -OC(O)O- can be directly connected to the triazine ring; and R2 and R3 are substituted and/or non-substituted C3-C10-cycloalkyl, which comprises at least one nitrogen atom in the ring structure; as thermal stabilizer and/or light stabilizer in polyolefins at temperatures at or above 150°C.
Description
Use of a low molecular weight triazine based compound as thermal / light stabilizer in polymers
The present invention relates to the use of low molecular weight triazine based compounds for increasing the resistance of polymers against degradation caused by heat and light; to polymer compositions with increased resistance to heat and light and to the use of such polymer compositions for producing articles.
Description
It is known that the mechanical, chemical and/or aesthetic properties of polymeric materials, worsen under the influence of energy such as heat and/or sunlight and other sources of ultraviolet (UV) radiation, and/or oxygen. This results in an irreversible deterioration of the chemical and/or physical properties of the non-living organic materials, e.g. results for polymeric materials i.a. in a loss of strength, stiffness and flexibility, discoloration and scratching and loss of gloss.
Such aging processes are normally based on oxidation reactions which are caused by heat, light, mechanical stress, catalysis or reactions with impurities. The aging of polymeric materials can occur during their production, during processing into shaped parts by moulding, extrusion, etc. and/or during use of the shaped parts.
It is well-known in the art that stabilizers, such as antioxidants, light stabilizers and heat / thermal stabilizers can prevent or at least reduce these effects by adding them to the polymers to protect them during processing and to achieve the desired end-use properties.
Antioxidants interrupt the degradation process in different ways, depending on their structure. The two major classifications are chain terminating primary antioxidants and hydroperoxide decomposing secondary antioxidants. Primary antioxidants react rapidly with peroxy radicals and are therefore called “radical scavengers”. The majority of primary antioxidants for polyolefins are sterically hindered phenols. Triazine based Mannich compounds have also shown to protect polyolefins against oxidative degradation and degradation caused by UV radiation (WO 2013/041592 A1 ). In contrast, phenolic compounds do not function well as light stabilizers.
The heat stabilizing effect of a compound is strongly influenced by the temperature the polymer is exposed to and the protection mechanism. For example, the polymer degradation at high
temperatures is mainly due to the oxidation of the polymer itself, while at low temperatures the secondary oxidation of (smaller) oxidation products such as aldehydes is more important.
Hindered amine light stabilizers (HALS) are chemical compounds containing an amine functional group that are used as stabilizers in plastics and polymers. HALS do not absorb UV radiation, but act to inhibit degradation of the polymer by continuously and cyclically removing free radicals that are produced by photo-oxidation of the polymer. Broadly, HALS react with the initial polymer peroxy radical (ROO) and alkyl polymer radicals (R·) formed by the reaction of the polymer and oxygen, preventing further radical oxidation. By these reactions HALS are oxidised to their corresponding aminoxyl radicals (R2NO c.f. TEMPO), however they are able to return to their initial amine form via a series of additional radical reactions. HALS's high efficiency and longevity are due to this cyclic process wherein the HALS are regenerated rather than consumed during the stabilization process.
HALS are capable of preventing the oxidation of aldehydes, but do not influence the oxidation rate of polymers (hydrocarbons). Thus, HALS are known as good heat stabilizers at low temperatures (P. Gijsman, Polymer Degradation and Stability, 1994, 43: 171 -176).
Compared to the phenolic antioxidants the main benefit of HALS when used as thermal stabilizers are 1 ) high efficiency up to certain temperatures; 2) no or low discoloring. In particular the low discoloring provides the unique opportunity of HALS for some applications, such as low (no) gas fading fibre, or medical devices where specific sterilization technique are used (e.g. gamma radiation). However, the key limitation is the application temperature of HALS stabilized compounds. In most cases, HALS has an effective thermal stabilizing effect upto a temperature of about Q 'Ό. Beyond that temperature the efficiency drops significantly and conventional HALS are not suitable for applications above I dO 'Ό anymore.
It was therefore an object of the invention to provide compounds that comprise the benefits of HALS and can be used as thermal stabilizer at higher application temperature (T >150°C).
This object is solved by the uses of a triazine based compound as defined in claim 1 .
Accordingly, the present invention relates to the use of a triazine based compound of the general formula (I)
wherein
- R1 is hydrogen, halogen, substituted or non-substituted hydroxy, substituted or non- substituted amino, substituted or non-substituted C5-C20 aryl, substituted or non-substituted, linear or branched Ci-Ci2-alkyl, substituted and non-substituted, linear or branched C2-C12- alkenyl, wherein Ci-Ci2-alkyl and C2-Ci2-alkenyl can be interrupted by one or more atoms or groups selected from oxygen atoms, substituted or mono-substituted nitrogen atoms, double bonds, siloxan groups and/or by one or more groups of the type -C(0)0-, -OC(O)-, -C(O)-, - C(0)NH-,-NHC(0)0-, -0C(0)NH-, -NHC(0)NH- and/or -00(0)0-, whereby the atoms and groups selected from oxygen atoms, -OC(O)-, -C(O)-, -NHC(0)0-, -NHC(0)NH- or -00(0)0- can be directly connected to the triazine ring; and
- R2 and R3 are substituted and/or non-substituted C3-Cio-cycloalkyl, which comprises at least one nitrogen atom in the ring structure; as thermal stabilizer and/or light stabilizer in polyolefins at temperatures at or above
150 <€.
Thus, a low molecular weight compound, in particular with a molecular weight < 2000, preferably < 1800, more preferably < 1500, most preferably < 1200, is provided that can be used as light stabilizer, but in particular as thermal and/or light stabilizer in thermoplastic polymers at temperatures above I dO 'Ό. The triazine based compound show an improved stability effect at temperatures above 150 'Ό when compared to conventionally used stabilizers such as 1 ,3,5-T ris(3’,5’-di-tert. butyl-4’-hydroxybenzyl)-isocyanurate (Irganox 31 14). Thermal and light stabilizing effects, in particular at temperatures above I dO 'Ό, can also be described as overlapping effects. The HALS of the present invention may also be described as having light stabilizing effects at different temperatures, in particular above I dO 'Ό. Thus, the HALS compounds of the present invention protect the polyolefin against thermo oxidative degradation.
The triazine based compound used in this invention have been described previously. DE 2319816 A1 discloses a family of triazine based HALS compounds used a light stabilizers in polymers. However, the use of such a triazine based compound as thermal stabilizer in polyolefins at elevated temperatures above I dO'Ό is not described. Furthermore, the triazine based compound of the invention has been used either as reactive substances, to create the high molecular weight HALS or with other polymers such as polyamid to form stabilized compositions. So far, no direct use of the triazine based molecules as thermal stabilizer in polyolefins is described.
In one embodiment the moiety R1 is hydrogen, halogen, substituted or non-substituted hydroxy, substituted or non-substituted amino, substituted or non-substituted C1-C5 alkyl, substituted or non-substituted C6-Ci2 aryl; and the moieties R2 and R3 are substituted and/or non-substituted C3-C7-cycloalkyl, which comprises at least one nitrogen atom in the ring structure.
In a further preferred embodiment the moiety R1 is from a group consisting of halogen, - OCH3, -OC2H5, substituted or non-substituted amino, methyl and phenyl. In a most preferred embodiment the moiety R1 is halogen, such as chlorine, fluorine or bromine, in particular chlorine, or a primary amino group.
In another embodiment the moieties R2 and R3 are substituted and/or non-substituted C3-C7- cycloalkyl, which comprises one or two nitrogen atoms in the ring structure.
In yet another embodiment the triazine based compound of the general formula (I) comprises the following structure (II)
wherein
- R1 has one the above meanings;
- R4 and R5 are selected independently from each other from substituted or non- substituted, linear or branched CrCis-alkyl, preferably substituted or non-substituted, linear or branched Ci-Cio-alkyl, and
- n is 0 to 8, preferably 2-4.
It is furthermore preferred if the triazine based compound of the general formula (I) comprises the following structure (III)
wherein
- R1 has one the above meanings;
- R4a d and R5a d are selected from substituted or non-substituted, linear or branched Cr C5-alkyl, preferably substituted or non-substituted, linear or branched C1-C3 alkyl.
Yet in a more preferred variant the triazine based compound of the general formula (I) comprises the following structure (IV)
wherein R1 has one the above meanings;
The term “substituted” in connection to aryl, alkyl, alkenyl and cycloalkyl relates to the substitution of one or more atoms, usually H-atoms, by one or more of the following substituents: halogen, hydroxy, protected hydroxy, oxo, protected oxo, C3-C7-cycloalkyl, phenyl, naphtyl, amino, protected amino, primary or secondary amino, heterocyclic ring, imidazolyl, indolyl, pyrrolidinyl, Ci-Ci2-alkoxy, Ci-Ci2-acyl, CrCi2-acyloxy, nitro, carboxy, carbamoyl, carboxamid, N-(Ci-Ci2-alkyl)carboxamid, N,N-Di(Ci-Ci2-alkyl)carboxamid, cyano, methylsulfonylamino, thiol, Ci-Ci0-alkylthio und Ci-Ci0-alkylsulfonyl. The substituted groups can be once or twice substituted with same or different substituents.
The term "substituted" in connection to hydroxy and amino relates to the substitution of at least one H atom by one or in case of amino one or two of one of the substituents mentioned above, in particular substituted and non-substituted, linear or branched Ci-Ci2-alkyl, substituted and non-substituted C3-C7-cycloalkyl and substituted and non-substituted, linear or branched C2- Ci2-alkenyl. Hence, the hydroxy group can be present as an ether group. Amino group can be present as a primary or secondary amine.
The term„alkyl“ relates to moieties like methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s- butyl, t-butyl, amyl, t-amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and alike. Preferred alkyl groups are methyl, ethyl, isobutyl, s-butyl, t-butyl und isopropyl.
The term“oxo” relates to a carbon atom, which is connected with an oxygen atom via a double bond whereby a keto or an aldehyde group is formed. The term“protected oxo” relates to a carbon atom, which is substituted by two alkoxy groups or is connected twice with a substituted diol forming a non-cyclic or cyclic ketal group.
The term„alkoxy“ relates to moieties like methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t- butoxy and alike. A preferred alkoxy group is methoxy.
The term „C3-C7-cycloalkyl“ comprises groups like cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl und cycloheptyl.
In an even more preferred embodiment the triazine based compounds have one of the following structures:
(3) (4) The preparation of the triazine based compound suitable as stabilizer can be done for example by reacting cyanuric chloride with 4-Amino-2,2,6,6-tetramethylpiperidine 6-Chloro-A/2,A/4- bis(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4-diamin (C21H38CIN7, 1 ), which may react further to A^,A/4-(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4,6-triamin (2). In a further embodiment the triazine based compound is used as thermal stabilizer and/or light stabilizer in polyolefins in a temperature range between 150‘O and 250 °C, preferably between I dO'Ό and 200‘O, more preferably between I QO'Ό and 180°C.
In still another embodiment the triazine based compound is added to the thermoplastic polymer in a concentration between 200 and 5000 ppm, preferably between 500 and 3000 ppm, more preferably between 1000 and 2000 ppm. The most preferred concentration range is between 350 - 2500 ppm.
Preferably the polyolefins to be stabilized are for example:
- polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut- 1 -ene, poly-4-methylpent-1 -ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example of cyclopentene or norbornene; furthermore polyethylene (which optionally can be crosslinked); for example, high density polyethylene (HDPE), polyethylene of high density and high molar mass (HDPE-HMW), polyethylene of high density and ultrahigh molar mass (HDPE-UHMW), medium density polyethylene (HMDPE), low density polyethylene (LOPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
-mixtures of the polymers mentioned above, for example mixtures of polypropylene with polyisobutylene, polyethylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE) with one another.
- Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-but-1 -ene copolymers, propylene-isobutylene copolymers, ethylene-but-1 -ene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene- octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene-acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned under 1 ), for example polypropylene-ethylene-propylene copolymers, LDPE-ethylene-vinyl acetate copolymers, LDPE-ethylene-acrylic acid copolymers, LLDPE-ethylene-vinyl acetate copolymers, LLDPE- ethylene-acrylic acid copolymers and alternating or random polyalkylenecarbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
Polyolefins, i.e. polymers of monoolefins exemplified in the preceding paragraphs, in particular polyethylene and polypropylene, can be prepared by various, and especially by the following, methods:
a) free-radical polymerization (normally under high pressure and at elevated temperature) b) catalytic polymerization using a catalyst that normally contains one or more metals of group IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls
and/or aryls that may be either p- or s-coordinated. These metal complexes may be in the free form or fixed on substrates, for example on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization or further activators may be used, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements of groups la, I la and/or Ilia of the Periodic Table. The activators may be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler-Natta, TNZ (DuPont), metallocene or single site catalysts (SSC).
In a preferred case the polyolefin is selected from polyethylen, polypropylen, high pressure polyethylene or copolymers thereof.
It is to be understood that halogenated polyolefins, in particular chlorinated polyeolefins, such as PVC, are excluded from the list of polyolefins. This is due to the fact that when heating halogenated polyolefins, such as PVC, hydrogen halides, such as HCI, are released which interact with the stabilizer and thereby reducing the amount of available stabilizer. Thus, typically, additional compounds are added to the halogenated polyolefins which interact with the released hydrogen halides. For example, organozinc compounds, in particular organozinc compounds containing a Zn-0 or a Zn-S bond, such as Zn-stearate, are used for such purposes.
Thus, in an embodiment non-halogenated polyolefins are preferably used. Furthermore, it is also to be understood that the polyolefins applied in the present case are free of any additional organometallic compounds that is not a catalyst or activator, in particular free of any organozinc compound.
The present invention, consequently, relates to a method of stabilizing a polyolefin against thermal and/or light degradation by incorporating an amount of a triazine based compound as defined above.
In addition, the present invention also relates to a polymer composition comprising a polyolefin and a triazine based compound as defined above.
The triazine based compound may be present in the polymer composition in a concentration between 200 and 5000 ppm, preferably between 500 and 3000 ppm, more preferably between 1000 and 2000 ppm. The most preferred concentration range is between 350 - 2500 ppm.
Depending upon their ultimate end use, the triazine based compounds of the formula (I) or mixtures therefrom of the present invention may be combined with a variety of additives conventionally employed in the antioxidant and/or UV stabilizing art, such as (further) anti oxidants, (further) UV absorbers and stabilizers, metal deactivators, antistatics, phosphites and phosphonites, hydroxylamines, nitrones, thiosynergists, co-stabilizers, nucleating agents, fillers and reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, level agents, optical brighteners, flameproofing agents, anti-static agents and blowing agents. Typical additives are described in the "Plastics Additives Handbook".
The triazine based compounds useful as stabilizer according to the present invention optionally in combination with a further stabilizer or additive may be added to the polyolefin to be stabilized individually or mixed with one another. If desired, the individual components of such a stabilizer mixture can be mixed with one another in the melt (melt blending) before incorporation into the polyolefin to be stabilized.
The incorporation of the triazine based compound of the invention and optional further components into the polyolefin is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil. The triazine based compounds of the invention and optional further additives may be incorporated, for example, before or after moulding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc), e.g. as a dry mixture or powder or as solution or dispersion or suspension or melt.
The incorporation can be carried out in any heatable container equipped with a stirrer, e.g. in a closed apparatus such as a kneader, mixer or stirred vessel. The incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.
The addition of the additive or additive blend to the polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable
machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
The process is preferably carried out in an extruder by introducing the additive during processing. Particularly preferred processing machines are single-screw extruders, contrarotating and corotating twinscrew extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied. Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, ISBN 3-446- 14329-7). For example, the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), very particularly preferably 25 - 300 rpm. The maximum throughput is dependent on the screw diameter, the rotational speed and the driving force. The process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts. If a plurality of components is added, these can be premixed or added individually.
The triazine based compounds of the invention and optional further additives can also be added to the polymer in the form of a masterbatch ("concentrate") which contains the components in a concentration of, for example, about 1 % to about 40% and preferably 2 % to about 20 % by weight incorporated in a polymer. The polymer need not be necessarily of identical structure than the polymer where the additives are added finally. In such operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
Incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. A further possibility for incorporating the additives of the invention into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking. In this context the additive of the invention can be added as it is or else in encapsulated form (for example in waxes, oils or polymers).
The polymer compositions, in particular the polyolefin compositions, containing the triazine based compounds of the invention described herein can be used for the production of
mouldings, rotomoulded articles, injection moulded articles, blow moulded articles, pipes, films, tapes, mono-filaments, fibers, nonwovens, profiles, adhesives or putties, surface coatings and the like. The invention is explained in more detail in the following examples.
Example 1 : 6-Chloro-A^,A/4-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4-diamin (HALS 2)
Cyanuric chloride reacts with 4-Amino-2,2,6,6-tetramethylpiperidine to 6-Chloro-A^,A/4- bis(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4-diamin (C21 H38CIN7), called HALS2, as shown in
Scheme 1 .
HALS2
Scheme 1 : Reaction to HALS2 2.766 g (15 mmol) of cyanuric chloride are dissolved in 30 cm3 deionized water and about 0.48 g (33 mmol) 25% NaOH solution are added. This solution is stirred for 20 minutes in an ice bath under argon atmosphere. 2.476 g (15.84 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine are dissolved in 7.3 cm3 acetone and added slowly. After a reaction time of 1 h, the solution is heated to 35 'Ό and again 2.448 g (15.66 mmol) of 4-Amino-2,2,6,6-tetramethylpiperidine dissolved in 7.3 cm3 acetone are added. The product is stirred for 2 hours at 35 °C and filtered
(suction filter, pore size 4) after cooling to room temperature. The filter cake is washed 3 x with 20 cm3 of deionized water and dried overnight in a drying oven at 60 qC. The product is a white, fine powder (4.7 g, 74%).
ESI- MS (m/z): 424 [HALS2+H]+, 212 [HALS2+2H]2+
Ή-NMR (300 MHz, CDCI3), 5 / ppm = 5,16-4,97 (m, 2H, -C-NH-CH-); 4,42-4,29 (m, 2H,-NH- CH-(CH2)2-); 1 ,97-1 ,92 (m, 4H,-CH-CH2-); 1 ,28-1 ,24 (m, 12H, -CH-(CH3)2); 1 ,13 (m, 12H, - CH-(CH3)2), 1 .00-0,92 (m, 6H,Ar-NH, -CH-CH2- ).
ATR-IR: v= 3208, 3075, 2404, 1700, 1489, 1474, 1415, 1400, 1360, 1316, 1258, 1062, 1051 , 976, 932, 877, 847, 790, 765, 745,692, 662, 645, 626, 61 1 , 597, 584, 578, 554, 551 cm 1
Mp.: (DSC, 10 Kmin 1)= 278 °C
DT: (DSC, 10 Kmin 1)= 341 °C
Example 2: A^,A/4-(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4,6-triamin (HALS 4)
HALS2 reacts with ammonia to A^,A/4-(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,3,5-triazin-2,4,6- triamin , called HALS4, as shown
Scheme 2.
Chemical Formula: C2IH38C1N Chemical Formula: CT IFEONJ Exact Mass: 423.29 Exact Mass: 404.34
Molecular Weight: 424.03 Molecular Weight: 404.61
HALS2 HALS4
Scheme 2: Reaction to HALS4
1 .399 g (3.45 mmol) of HALS2 are dissolved in 30 cm3 water and 0.62 cm3 (0.45 g, 6.64 mmol) ammonia (25%) are added. This solution is stirred for 3 hour at 80 °C under argon atmosphere. The product is filtered off (suction filter pore size 4) and dried overnight in a drying oven at 60 °C.
ESI- MS (m/z): 406 [HALS4+H]+, 424 [HALS2+H]+, 212 [HALS2+2H]2+
1H-NMR (300 MHz, CDCI3), 5 / ppm = 5,06-4,93 (m, 2H, -C-NH-CH-); 4,37-4.34 (s, 2H, ,-NH- CH-(CH2)2-); 1 ,94 (d, J=9,7 Hz, 4H, ,-CH-CH2-); 1 ,37-0,96 (m, 32H, -OH-(OH3)2, Ar-NH, -CH- CH2-, -NH2 ).
ATR-IR: v= 3254, 2994, 2960, 2960, 2929, 2882, 2863, 1673, 1613, 1603, 1549, 1458, 1423, 1386, 1379, 1357, 1310, 1289, 1270, 1238, 1210, 1 193, 1 163, 1 106, 1078, 1010, 979, 965, 943, 920, 849, 804, 796, 779, 701 , 671 , 642, 633, 616, 610, 599, 589, 577, 552 cm 1
Mp.: (DSC, 10 Krnirr1) =275 °C
DT: (DSC, 10 Krnirr1) =294 °C
Example 3: OIT-measurements
According to ISO 1 1357-6, the oxidative induction time (OIT) is the measured time in which the oxidation of a sample is inhibited by an existing antioxidant stabilizer system.
The OIT is measured while the sample is kept constant at a certain temperature under an oxygen stream. The measurement is performed in a differential scanning calorimeter (DSC). The sample and the reference are heated under constant nitrogen atmosphere to a specific temperature. When this temperature is reached, the gas flow switches to oxygen at the same flow rate. Until the oxidative degradation starts, the material is held at a constant temperature. The OIT is represented on a thermal curve. It is the time span between the start of the oxygen and the onset of the oxidative degradation reaction. The onset is indicated by a sudden change in heat flow.
The OIT measurements are carried out according to ISO 1 1357-6 on a Mettler Toledo DSC822e. The measurements are done with open pans.
Sample preparation: 0.2 wt% active group equivalent are mixed into Squalane (SQ). Squalane is used as matrix material due to its chemical similarity to PP and the easier handling. The structure is shown in Scheme 3. The stabilizer and SQ are first mixed in an ultrasonic bath and then with stirring to afford a homogenous suspensions.
Scheme 3: Structure of squalane (SQ)
Temperature Program Mettler Toledo DSC822e:
1 . Heat from 40 'Ό to 160°C(or 135 °C), 20 °C/ min, N2
2. Hold 5 min at 190‘O, N2
3. Switch to 02
The measurement is stopped when the degradation starts. The degradation is indicated with a sudden change in the heat flow curve indicating an exothermal process. The OIT-curves for HALS2 and HALS4 at 160 °C are shown in Table 1 .
Tinuvin 770 Bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate) and Irganox 31 14 (1 ,3,5-T ris(3’,5’- di-tert. butyl-4’-hydroxybenzyl)-isocyanurate) are used as comparative examples CE1 and CE2, respectively.
Table 1 lists the OIT of Inventive Examples (lEs) and Comparative Examples (CEs). Surprisingly it was found that by proper design the molecules, the IE do not work only at low T (like I Od'Ό), but also works at higher T (like 160°C), which is typically not the case of HALS and rather on the same level as phenolic antioxidants.
Table 1 : OIT of IE and CEs
Claims
1 . Use of a triazine based compound of the general formula (I)
wherein
- R1 is hydrogen, halogen, substituted or non-substituted hydroxy, substituted or non-substituted amino, substituted or non-substituted C5-C20 aryl, substituted or non- substituted, linear or branched Ci-Ci2-Alkyl, substituted and non-substituted, linear or branched C2-Ci2-alkenyl, wherein Ci-Ci2-alkyl and C2-Ci2-alkenyl can be interrupted by one or more atoms or groups selected from oxygen atoms, substituted or mono- substituted nitrogen atoms, double bonds, siloxan groups and/or by one or more groups of the type -C(0)0-, -OC(O)-, -C(O)-, -C(0)NH-,-NHC(0)0-, -0C(0)NH-, -NHC(0)NH- and/or -00(0)0-, whereby the atoms and groups selected from oxygen atoms, -OC(O)-, -C(O)-, -NHC(0)0-, -NHC(0)NH- or -00(0)0- can be directly connected to the triazine ring; and
- R2 and R3 are substituted and/or non-substituted C3-Cio-cycloalkyl, which comprises at least one nitrogen atom in the ring structure; as thermal stabilizer and/or light stabilizer in polyolefins at temperatures at or above 150 °C.
2. Use according to claim 1 , wherein
- R1 is hydrogen, halogen, substituted or non-substituted hydroxy, substituted or non-substituted amino,; and
- R2 and R3 are substituted and/or non-substituted C3-C7-cycloalkyl, which comprises at least one nitrogen atom in the ring structure.
3. Use according to one of the preceding claims, wherein R1 is from a group consisting of halogen, - OCH3, -OC2H5, substituted or non-substituted amino, substituted or non- substituted C1 -C5 alkyl, substituted or non-substituted C6-Ci2 aryl.
4. Use according to one of the preceding claims, wherein R2 and R3 are substituted and/or non-substituted C3-C7-cycloalkyl, which comprises one or two nitrogen atoms in the ring structure.
5. Use according to one of the preceding claims, wherein the triazine based compound of the general formula (I) comprises the following structure (II)
wherein
- R1 has one the above meanings;
- R4 and R5 are selected from substituted or non-substituted, linear or branched C1-C18- alkyl, preferably substituted or non-substituted, linear or branched Ci-Cio-alkyl, and
- n is 0 to 8, preferably 2-4.
6. Use according to one of the preceding claims, wherein the triazine based compound of the general formula (I) comprises the following structure (III)
wherein
- R1 has one the above meanings;
- R4a d and R5a d are selected from substituted or non-substituted, linear or branched Cr
C5-alkyl, preferably substituted or non-substituted, linear or branched C1-C3 alkyl.
7. Use according to one of the preceding claims, wherein the triazine based compound of the general formula (I) comprises the following structure (IV)
wherein R1 has one the above meanings; 8. Use according to one of the preceding claims, wherein the triazine based compound of the general formula (I) has a molecular weight < 2000, preferably < 1800, more preferably < 1500, most preferably < 1200.
9. Use according to one of the preceding claims, wherein the triazine based compound is used as thermal stabilizer and/or light stabilizer in thermoplastic polymers, in particular in polyolefins, in a temperature range between 150°C and 250‘O, preferably between I dO 'Ό and 200‘O, more preferably between I QO 'Ό and 180°C.
10. Use according to one of the preceding claims, wherein the triazine based compound is added to the thermoplastic polymer in a concentration between 200 and 5000 ppm, preferably between 500 and 3000 ppm, more preferably between 1000 and 2000 ppm.
1 1 . Use according to one of the preceding claims, wherein the polyolefin is selected from polyethylene, polypropylene, high pressure polyethylene or copolymers thereof; and/or the polyolefin is a non-halogenated polyolefin; and/or the polyolefin is free of any organozinc compound.
12. Method of stabilizing a polyolefin against thermal and/or light degradation by incorporating an amount of a triazine based compound as defined in one of the claims 1 -8.
13. Polymer composition comprising a polyolefin and a triazine based compound as defined in one of the claims 1 -8.
14. Polymer composition according to claim 13, wherein the triazine based compound is present in a concentration between 200 and 5000 ppm, preferably between 500 and 3000 ppm, more preferably between 1000 and 2000 ppm.
15. Use of a polymer composition according to claim 13-14 for the production of mouldings, rotomoulded articles, injection moulded articles, blow moulded articles, pipes, films, tapes, mono-filaments, fibers, nonwovens, profiles, adhesives or putties, or surface coatings.
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|---|---|---|---|
| EP18195484 | 2018-09-19 | ||
| PCT/EP2019/075010 WO2020058338A1 (en) | 2018-09-19 | 2019-09-18 | Use of a low molecular weight triazine based compound as thermal / light stabilizer in polymers |
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| GB1393551A (en) | 1972-04-21 | 1975-05-07 | Ciba Geigy Ag | Piperidine derivatives |
| TW321658B (en) * | 1992-09-17 | 1997-12-01 | Ciba Sc Holding Ag | |
| US5804622A (en) * | 1996-03-22 | 1998-09-08 | Ciba Specialty Chemicals Corporation | Monomeric N-piperidinylmelamines as stabilizers for chlorine-containing polymers |
| KR20140069132A (en) | 2011-09-23 | 2014-06-09 | 보레알리스 아게 | Stabilizing of organic material with amino-triazine based mannich-compounds |
| CN104140556B (en) * | 2014-08-13 | 2017-01-18 | 北京天罡助剂有限责任公司 | Triazine compound with photooxidation resistance and heat oxidation resistance and synthesis method thereof |
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2019
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