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In this work pyrolysis-GC/MS studies are presented on two pairs of hindered amine light stabilisers (HALS) oligomers and polymers. Pyrolysis has been performed in the temperature range from 300 to 900C, also in the presence of PVC in order to observe the possible effect of this hardly avoidable plastic waste component on the production of volatiles from HALS compounds. Intramolecular rearrangement of ester segments of the macromolecular chain leads to succinic acid anhydride and 1-azacyclohexeneethanol in Tinuvin 622 already at 400C. In the presence of PVC 1-azacyclohexenechloroethane is also formed from this stabiliser. The piperidine moieties bound to the macromolecular core by ester bonds are cleaved through unimolecular beta-elimination reaction at around 500C. Thermal decomposition of HALS composed of only amines starts at higher temperatures and proceeds through the scission of C-N bonds. Alkenes are cleaved from secondary amino groups more easily than from tertiary ones. The scission of the pirimidine ring leads to alkylenamines, alkadienes and trienes at above 600C. In the presence of PVC the formation of alkylenamines is depressed. By C-C bond cleavage volatile products originating from alkyl side groups or hindered phenolic moieties also appear in the pyrolysate. Aromatisation of the piperidine rings with methane loss takes place at above 700C leading to 2,6-dimethylpyridine, 2,6-dimethylanilines and 1,3-dimethylbenzene. In the presence of PVC the formation of pyridine and aniline compounds are depressed. At 900C volatile alkane- and alkenenitriles evolve together with traces of hydrogen cyanide. The formation of hydrogen cyanide is enhanced in the presence of PVC.

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Reference:
Piperidine – Wikipedia,
Piperidine | C5H10369N – PubChem

 

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Hindered Amine Light Stabilizers (HALS), N-methylated and O-alkylhydroxylamine, were successfully anchored onto an ethylene-co-butyl acrylate (BA) by a transesterification reaction in the molten state. The content of HALS bonded to the EBA was calculated from the atomic ratio (N/C) determined by X-ray Photoelectron Spectroscopy (XPS). After reaction times of 5-30 min in the molten state the content of bonded HALS attained values from 0.17 to 0.63%. The modified EBA with HALS were studied by Chemiluminescence emission and the photostabilization effect was evaluated under accelerated ageing in the presence of pesticides. The antioxidant effect of HALS bonded to EBA was evaluated by determination of Carbonyl Index (CI) and retention of elongation at break as a function of exposure time and pesticide treatment. The stability of the EBA with anchored HALS exhibited higher performance as shown by low CI-values and correlated with the content of bound HALS and the thermal history of the materials. Also, mechanical properties correlated well with the CI results and the photostabilization of bound HALS was effective until 3150 h of exposure time using pesticides.

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Piperidine – Wikipedia,
Piperidine | C5H10372N – PubChem

 

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Piperidine derivatives, their production and use as stabilizers

The present invention relates to a piperidine derivative represented by the general formula (I), STR1 wherein R1 and R2 independently represent a hydrogen atom or a C1 -C3 alkyl or C2 -C20 acyl group, R3 represents a hydrogen atom or a C1 -C20 alkyl, C6 -C20 aryl, C7 -C20 aralkyl or C2 -C20 acyl group, and l represents 1 to 3, and a stabilizer for organic substances containing said piperidine derivative as an effective ingredient.

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Hindered amine-substituted dihydropyridines and heat/light stabilization of polymer substrates therewith

Novel dihydropyridine compounds bearing substituted piperidyl substituents are effective heat/light stabilizers for a wide variety of polymer substrates, e.g., for halopolymers such as PVC, and are also effective anti-UV agents and antioxidants for such polymers as polyolefins, polystyrenes, polyalkadienes, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyethersulfones, polyetherketones, acrylic polymers, or copolymers or mixtures thereof.

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Piperidine – Wikipedia,
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Piperidine derivatives, their production and use as stabilizers

The present invention relates to a piperidine derivative represented by the general formula (I), STR1 wherein R1 and R2 independently represent a hydrogen atom or a C1 -C3 alkyl or C2 -C20 acyl group, R3 represents a hydrogen atom or a C1 -C20 alkyl, C6 -C20 aryl, C7 -C20 aralkyl or C2 -C20 acyl group, and l represents 1 to 3, and a stabilizer for organic substances containing said piperidine derivative as an effective ingredient.

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Piperidine – Wikipedia,
Piperidine | C5H10319N – PubChem

 

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Hindered amine-substituted dihydropyridines and heat/light stabilization of polymer substrates therewith

Novel dihydropyridine compounds bearing substituted piperidyl substituents are effective heat/light stabilizers for a wide variety of polymer substrates, e.g., for halopolymers such as PVC, and are also effective anti-UV agents and antioxidants for such polymers as polyolefins, polystyrenes, polyalkadienes, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyethersulfones, polyetherketones, acrylic polymers, or copolymers or mixtures thereof.

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Piperidine – Wikipedia,
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Novel blue emitting tetra- and pentamethylpiperidin-4-yloxy-1,8-naphthalimides as photoinduced electron transfer based sensors for transition metal ions and protons

Two novel blue emitting 1,8-naphthalimides (1 and 2), containing 2,2,6,6-tetramethylpiperidin-4-yloxy moieties, and newly synthesized under phase transfer catalysis conditions 4-(1,2,2,6,6-pentamethylpiperidin-4-yloxy)-1,8-naphthalimide 7, were configured as “fluorophore-spacer-receptor” systems. Basic photophysical characteristics of the novel fluorescent brighteners were investigated in both DMF and water/DMF (4:1, v/v) solution. Their ability to detect cations was evaluated in the presence of transition metal ions (Cu2+, Pb2+, Zn2+, Ni2+, Co2+) and protons. The presence of metal ions and protons was found to disallow a photoinduced electron transfer leading to an enhancement in the fluorophore emission intensity. The results clearly showed a good sensor activity towards transition metal ions and protons, especially of compound 7, containing tertiary amine receptor. This indicates the potential of the novel compounds as highly efficient “off-on” pH switchers and fluorescent detectors for metal ions.

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Synthesis and characterization of core-shell polyacrylate particles containing hindered amine light stabilizers

A polymerizable hindered amine light stabilizer (HALS) 1,2,2,6,6-pentamethylpiperidin-4-yl acrylate (PMPA) was synthesized through transesterification of 1,2,2,6,6-pentamethylpiperidin-4-ol (PMP) with methyl acrylate (MA). Core-shell latex particles containing HALS moieties in the shell phase were prepared by two-stage seeded emulsion polymerization from n-butyl acrylate (BA), methyl methacrylate (MMA) and PMPA. The Fourier transformed infrared (FTIR) and nuclear magnetic resonance (1H NMR) analysis showed that PMPA monomer was successfully prepared and was effectively involved in the polyacrylate particles. The surface composition was studied by X-ray photoelectron spectroscopy (XPS), and the results indicated that HALS-containing groups could be distributed on the surfaces of the particles. Transmission electron microscopy (TEM) analysis revealed that the particles obtained presented a core-shell structure with a particle size around 100nm. Two glass transition temperatures (Tg), assigned to the core phase and the shell phase of the particles, respectively, were observed for both HALS-containing and HALS-free particles, as determined by differential scanning calorimetry (DSC). In addition, the Tg value for the shell phase of HALS-containing particles was 13C lower than that of HALS-free particles, indicating the presence of random copolymer between MMA monomer and PMPA comonomer in the shell phase. The thermogravimetry analysis (TGA) and differential thermal gravimetric (DTG) results showed that HALS-containing particles provided an improvement in thermal stability in comparison to HALS-free particles.

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STABILIZER COMPOUNDS

A piperidine-based stabilizer compound of formula (I) or (II) that imparts UV, thermal, and/or thermo-oxidative stability to polymer compositions and more specifically to aromatic polymers and polymer compositions thereof.

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Piperidine – Wikipedia,
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Piperidine derivatives

New piperidine derivatives of 1,3-pyrimidine and 1,3,5-triazine are used as stabilizers for organic materials, especially for polymers.

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Piperidine – Wikipedia,
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