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Optimization of Flame Retarded PP-Copolymer Compounds. By: Or Kariv Advisors: Dr. Fabian Rios Yoav Bar-Yaakov, Bromine Compounds LTD. Objectives. Finding an optimal formulation of PP copolymer with bromine based FR. Studying the influence of the FR on the compound’s properties.

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Optimization of flame retarded pp copolymer compounds

Optimization of Flame RetardedPP-Copolymer Compounds

By: Or Kariv

Advisors: Dr. Fabian Rios

Yoav Bar-Yaakov, Bromine Compounds LTD.


  • Finding an optimal formulation of PP copolymer with bromine based FR.

  • Studying the influence of the FR on the compound’s properties.

  • Studying the influence of IM processing conditions on the compound.


  • PP is known for its good mechanical and processing properties, but also for its high flammability.

Bromine FRs

  • C-Br present low bonding energy and therefore Br can readily be released.

  • FR molecular structure depends on the thermal stability required for the polymer.

    Aromatic compounds high thermal stability

    Aliphatic compounds high flame retardant efficiency

Fr properties


Tris- tribromoneopentyl phosphate

  • Thermal stability fits polymer processing temperature

  • Good synergy with the matrix

  • Good dispersion within the matrix

  • Non “blooming”

  • Good flame retardancy

  • Chemical flame inhibiting mechanism

Optimization of flame retarded pp copolymer compounds


Chain Scission & Flame poisoning: a competing reaction of HBr, with the radicals to create a less reactive radicals.


  • Materials:

    • PP copolymer- grade SE- 50E ex by Carmel Olefins

    • FR-370- Tris- tribromoneopentyl phosphate by Bromine Compounds Ltd.

    • Free radical source (C-C initiator)

  • Equipment:

    • Injection molding machine, Arburg 500-150

    • Twin-screw extruder, Berstroff L/D=32

  • Optimization of flame retarded pp copolymer compounds


    • Studying the influence of additives.

    • Optimized formulation:

    • UL-94: V-0 rating

    • Minimum additives content

    • Optimal balance of properties

    • Studying the effect of IM conditions.

    Stage one-

    Stage two-

    Optimization of flame retarded pp copolymer compounds

    Stage one:

    Selecting the optimal formulation

    Reference formulations:

    Results flammability properties
    Results: Flammability Properties

    LOI- limited oxygen index

    • Significant increase in the presence of FR

    • C-C influence insignificant.

    Results thermal properties
    Results: Thermal Properties

    HDT- heat deflection temperature

    • FR exhibits a significant increase of HDT

    • C-C has inverse effect

      by causing the crystallinity degree to decrease

    Results rheological properties
    Results: Rheological Properties

    MFI- melt flow index

    • FR exhibits a plasticizing effect in high temperature

    • C-C causes MW reduction

    Results mechanical properties
    Results: Mechanical Properties

    Izod impact test

    • The FR causes a significant decrease of impact strength

      Particles locate at amorphous phase and cause stress concentration

    Results mechanical properties1
    Results: Mechanical Properties

    Tensile modulus

    • FR causes a stiffening effect at room temperature

    • C-C causes MW reduction


    Choosing optimal formulation

    Balance between additives concentrations and properties

    Minimum costs

    Formulation Hcc14:

    14% Br, 1.6% C-C

    Stage two doe for injection molding conditions
    Stage two:DOE for injection molding conditions

    • Formulations: Hcc14 and 0cc20.

    Independent variables:

    • A- Screw RPM

    • B- Back pressure

    • C- Injection speed

    • D- Melt temperature

    • E- Mold temperature

    • F- Holding pressure

      Dependant variables:

    • Tensile strength

    • Tensile modulus

    • Impact strength

    • DSC: melting temperature

      melting enthalpy

    A six variables, two level screening design

    Optimization of flame retarded pp copolymer compounds


    • No reliable results were obtained from the experiment.

      The reason

    • Experimental error larger than variables effects.

    • Little control over formulations processing.


    • Plasticizing effect of the FR on polymer causing difficult processing.

    Doe results
    DOE results

    Smaller than experimental error → 0

    Marginal → 0


    • FR content affects polymer properties significantly.

    • FR content can be reduced by adding free radical source while maintaining flammability level.

    • Mechanical and rheological properties decrease.

    • Thermal properties increase.

    • An optimal formulation for flame retardant PP copolymer contains 14% Bromine (20% FR-370) and 1.6% C-C initiator.

    • While these compounds exhibit good FR properties, they are extremely difficult to process, limiting their commercial applications.

    • DOE analysis can be performed only on fully controllable processes.

    Further research
    Further Research

    • More extensive research on the rheological properties of PP copolymer- FR compounds is required, using capillary and dynamic rheometers.

    • A capillary rheometer will show how viscosity changes with higher shearing rates similar to IM process, as opposed to MFI.

    • The processing problems of these compounds should be addressed, researched and improved to obtain compounds which are more commercially usable.

    For all the help and support
    For all the help and support…

    Ita Finberg, Yaniv Hirschsohn, Izik, Meir & Smadar

    Dr Iftah Nir, Dr Amos Ofir & Dr Anna Dotan

    And especially to

    Dr Fabian Rios from Shenkar

    Yoav Bar- Yaakov and Racheli Rotem from ICL-IP



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