FLAME LIGHT UV RETARDANTS ANTIOXIDANTS STABILIZERS ABSORBERS PLASTIC ADDITIVES TAILOR MADE FORMULATIONS GREENCHEMICALS POLICY OUR GOAL is to develop and promote improved Flame Retardant solutions! Environmental friendly: Halogen free, with low dosage, dust free, migration free. CONTENTS OUR FLAME RETARDANTS PRODUCTS: Masterbatches, powder blends, compacted blends, cold extruded pellets, dropped beads. BROMINATED FLAME RETARDANTS PAG. 08 HALOGEN FREE FLAME RETARDANTS PAG. 10 MASTERBATCHES POWDER BLENDS COMPACTED BLENDS COLD EXTRUDED LIQUID DISPERSIONS INORGANIC FLAME RETARDANTS PAG. 13 PELLETS FLAME RETARDANTS FORMULATIONS PAG. 14 MAIN ACTIVITIES: OTHER PRODUCTS: • XPS, EPS, X-EPS • Antioxidants ANTIOXIDANTS PAG. 16 • XPE, XPU • Uv • Engineering Thermoplastics • Processing aids • Reactive flame retardants • Colors. UV ABSORBERS - LIGHT STABILIZERS PAG. 18 ONE SHOT FORMULATIONS PAG. 21 GREENCHEMICALS is very active in the substitution of SVHC molecules and provides optimized solutions considering: OPTICAL BRIGHTENERS PAG. 22 • Fire Performance and thermal stability • Superior Environmental and health profile (more sustainable) SMA PAG. 22 • Compatibility with polymeric matrix • Cost/Performance PROCESS AID & STABILIZERS PAG. 22 GREENCHEMICALS Srl complies with REACH, CLP, SVHC, Food Contact, RoHS PROCESS AID & PEROXIDES PAG. 23 regulations and is determined to pursue the continuous improvement in all aspects of its work. QUALITY MANAGEMENT SYSTEM Greenchemicals’ decision to adopt a Quality Management System (QMS) of ISO 9001 is to improve the ability to integrate and coordinate all activities associated with the quality. To allow a better Family management, GreenChemicals, since the beginning, supports smart working, part time and flexible working time. MEMBERSHIP: 02 03 FLAME RETARDANT MECHANISM MECHANISM: 1· GAS PHASE Flame retardants are substances which may reduce flammability of materials by Brominated flame retardants interrupt the radical chain mechanism of the combustion process in the interaction with the fire cycle (FIGURE 1) in order to prevent, delay or stop it. gas phase thanks to generation of lower energy halogen radicals and dilution of flammable gases. Flame retardants act at different stages, depending on their chemical basis. HBr + OH• → H2O + Br• ( 4 ) ( 5 ) HBr + •O• → OH• + Br• H* HX COMBUSTION OH* HOH H-H O* X* HBr + H• ↔ H2 + Br• O2 O2 Combustion is a chemical reaction of oxidation CO HX CO CO CO that involves heat, flames and smoke/gases with HBr + RCH2• ↔ RCH3 + Br• 2 2 RBr ↔ OH• + Br• POLYMER POLYMER ( 4 ) Without Flame Retardant generation of high energy radicals. ( 1 ) + R-X ( 5 ) With Halogenated Flame Retardant CO + OH• → CO2 + H• 2· CHAR RCH3 + OH• → RCH2• + H2O Flame retardancy is obtained by formation of a solid charred surface layer of phosphorus compounds. The flame retardant is transformed into phosphoric acid by thermal degradation in the condensed RCH2• + O2 → RCHO + OH• phase, and water is released from the substrate in the solid phase developing protective layer: char. H• + O2 → OH• + •O• >250°C ( 6 ) ( 7) The fire starts with an ignition source put on combustible item. Solid materials do (NH4PO3)n (HPO3)n HEAT HEAT not burn directly, they are degradated by heat due to : polymer’s long-chain -n NH3 COMBUSTION Pyrolysis O2 molecules are decomposed into smaller ones, with the emission of flammable gases in theGas VOLATILES Phase and the formation of inert carbonised material in the Condensed Phase, char. (FIGU- (HPO3)n +Cx(H2O)m (“C”)x+(HPO3)n x mH2O RE 2) In the gas phase visible flames are generated by reaction of flammable gases with oxygen. POLYMER PROTECTIVE ( 6 ) Without Flame Retardant High energy exothermic chemical reactions take place and generate heat energy that supports LAYER ( 7 ) With Flame Retardant combustion. 3· INTUMESCENT ( 2 ) Intumescent mechanism provides efficient flame retardancy to polymers who do not contain heteroatoms in the chain. Char layer is not sufficient and a foaming agent is required to obtain a voluminous protective layer. Intumescent flame retardant systems consist of: · Carbon agent · Acid based on phosphorous · Compound containing nitrogen HEAT HEAT HEAT FLAME RETARDANTS H2N N NH2 Flame retardants prevent or even suppress the process of combustion during a particular phase of the Δ O2 N N NH3 N2 + H2O fire cycle:heating, decomposition, ignition, flame spread. Flame retardant action can be physical or chemical (FIGURE 3). NH2 POLYMER CHAR INTUMESCENT CHAR MECHANISM WAY EFFECT ( 3 ) 4· DRIPPING Cooling WATER VAPOR PHYSICAL Flame retardant decomposes into radical species that cut polymers chain and cause dripping of the Release of water vapor polymer. The reaction is endothermic. GAS PHASE CHEMICAL Release of inert gases Cooling -CH2-CHX-|-CH2-CHX* CH2-CHX* + CH2=CHX CHAR CHEMICAL / PHYSICAL ZONE OF Char Layer FLAME Oxygen Cooling Water release: INTUMESCENT CHEMICAL / PHYSICAL Expanded Char Layer ENERGY - cooling of 5· WATER VAPOUR material surface Polymer Chain Scission - diluition of DRIPPING CHEMICAL Flame retardancy is provided by water release. burnable gases Endothermic reaction cools material surface IGNITION Water Chemical reaction can occur: and dilute burnable gases with formation of a SOURCE PREFLAME · In the gas phase by cooling the system and reducing flammable gases. charred layer. Primary Secondary decomposition ZONE decomposition ENERGY · In the condensed phase by generation of a char layer providing a barrier against the heat source ENERGY OXYDE Physical action can take place by : Reduction of fire energy Formation of an 2Al(OH)3 Al2O3 + 3 H2O oxide layer · Cooling : release of water that cools the underlying substance Mg(OH)2 MgO + H2O · Coating : formation of solid or gaseous layer that protects material 2 AlOOH Al2O3 + H2O · Dilution : dilution of the fuel by formation of non-combustibile gas 04 05 ANTIOXIDANTS UV ABSORBERS / LIGHT STABILIZERS ANTIOXIDANTS CYCLE UV STABILIZERS Weathering of polymers is caused by absorption of UV lights, which results in radical initiated UV stabilizers are chemical compounds capable of interfering with the physical and chemical processes auto-oxidation by contact with athmospheric oxygen and generation of free radicals such as R•, RO•, of light-induced degradation. They prevent the formation of free radicals that can be generated by ROO•, HO•. These free radicals further react with atmospheric oxygen to produce more and more free interaction of UV radiation with tertiary carbon bonds in polymer chain structures or with aromatic radicals. rings. They can act in different ways: R• + O2 ROO• R·H (Polymer) UV ABSORBERS Polymer ROO• + R-H ROOH + R• UVA HEAT UV Light Antioxidants inhibit the formation of free radicals, enhancing the stability of polymers against light and heat, by termination of the oxidation reactions that involve polymers: Catalysts R·H (Polymer) residue ROOH RO ·+· OH Polymer NIQ P-NOR UV LIGHT RH (Polymer) PATH OF R · Excited state DEGRADATION MANAGEMENT +HALS (P-NO-) Energy: Shear HALS HALS +O2 + R* Melt Processing RADICAL CONTROL +RH Catalyst Residues PATH OF Polymer Oxygen STABILIZATION ROO · R ·+ROH+H O Cycle 2 Cycle 1 2 RO*+*OH ROO* +HALS (P-NO-) · O-O · UVA Cycle 2 Cycle 1 R*+ +RH R’OH+RO+P·NO· RO ·+· OH R·+ROOH ROO· HALS ROOH ( 1 ) Photo-oxidation ( 2 ) Light stabilizer mechanism • UV ABSORBERS, usually dihydroxybenzophenones and hydroxyphenyl benzotriazoles, act by absorbing the UV radiation and dissipating the energy as low-level heat by reversible intramolecular proton transfer during which a quinone structure is formed. Phenolic AŎs react with free radicals to Phosphites react with hydroperoxides Phenolic AŎs react with yield inactive products (ROH and H 2 O) to yield inactive products (ROH) oxygen centered radicals R N R N • PRIMARY O N hv O N Hydrogen-donating antioxidants (AH), such as hindered phenols, quinone based compounds, N N OH O piperidinoxyl based compounds and secondary aromatic amines, inhibit oxidation by competing H with organic substrate (RH) for peroxy radicals, thereby interfering with the chain propagation step. ROO• + AH ROOH + A• • QUENCHERS are energy tranfer agents, they deactivate excited states of chromophoric groups in polymers before bond scission can occur, by energy transfer process or chemical and/or physical ROO• + RH ROOH + R• deactivation. • SECONDARY • HINDERED AMINES are derivatives of 2,2,6,6-tetramethyl piperidine and they slow down Secondary antioxidants based on phosphites (A) or sulphides like dialkyldithiocarbamates, the photochemically initiated degradation reaction through a cyclic process. They scavenge dialkyldithiophosphates and thiobisphenolates (B) prevent peroxide radicals formation as they radicals by the formation of nitroxyl radicals (R-O•) that combine with free radicals in polymers decompose hydroperoxides. generating aminoether molecules. These will then react with peroxides regenerating the nitroxyl radicals. (A) (B) O R· POOH + R S R P OH + R S R UV, O2 ROOH + P(OR1)3 ROH + O=P(OR1)3 1 N-R 2 N-O· 3 N-OR O O POOH + R S R P OH + R S R O R’OH+R=O R’OO· 06 07 BROMINATED FLAME RETARDANTS BROMINATED FLAME RETARDANTS M.P./S.R. M.P./S.R. PRODUCT NAME CHEMICAL FORMULA APPLICATION TGA PRODUCT NAME CHEMICAL FORMULA APPLICATION TGA Viscosity Viscosity GC DPE 81 Polyolefins - Engineering 350°C 1% @ 332°C GC PHT DIOLO HV Reaction products Rigid Polyurethane Foam, 15000 Decabromodiphenyl ethane thermoplastics. 5% @ 365°C of tetrabromophthalic anhydride with Urethane Elastomers and 30000 cps CAS n. 84852-53-9 High efficiency, dioxine free, 10% @ 378°C 2,2’-oxydiethanol and methyloxirane Coatings with high bromine PHYSICAL FORM: GR, PW multi-function for PE, PP, CAS n. 77098-07-8 content (Viscosity 25°C, HIPS, PA, PBT, EPOXY, PHE. PHYSICAL FORM: LIQ CP 15,000-30,000). GC DECA 83 Polyolefins - Engineering 305°C 1% @ 320°C GC PHT DIOL0 MV Reaction products Rigid Polyurethane Foam, 30000 Decabromodiphenyl oxide thermoplastics. 5% @ 365°C of tetrabromophthalic anhydride with Urethane Elastomers and 70000 cps CAS n. 1163-19-5 High efficiency, multi- 10% @ 387°C 2,2’-oxydiethanol and methyloxirane Coatings with high bromine PHYSICAL FORM: GR, PW function for PE, PP, HIPS, CAS n. 77098-07-8 content (Viscosity 25°C, PA, PBT, EPOXY, PHE.