Presented By Allan Dixon Page # Month/Year Author/BTC CONFIDENTIAL - - PowerPoint PPT Presentation

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Presented By Allan Dixon Page # Month/Year Author/BTC CONFIDENTIAL - - PowerPoint PPT Presentation

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May 2017 BASF and BTC Supporting the Environment & The Future Of The Rubber Market. Presented By Allan Dixon Page # Month/Year Author/BTC CONFIDENTIAL BTC products for the rubber market Colouration of Rubber Process

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Author/BTC Month/Year CONFIDENTIAL Page ‹#›

BASF and BTC Supporting the Environment & The Future Of The Rubber Market.

Presented By Allan Dixon

May 2017

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Author/BTC Month/Year CONFIDENTIAL Page 2

BTC products for the rubber market

  • Colouration of Rubber
  • Process stabilisation for rubber.
  • Light stabilisation
  • Other products for the rubber market
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Author/BTC Month/Year CONFIDENTIAL Page 3

Polymerisation Warehousing & storage Manufacture of finished product Application & end use

Process Stabilisation Whatever was put in during processing Compound stabilisers Whatever was put in during compounding To survive production:

  • Catalysts
  • Heat
  • Shear
  • Tamol –

emulsion process only

  • Pluriol etc.
  • Antioxidants

Long term Storage:

  • Gel
  • Colour
  • Storage
  • Viscosity

Production economies (e.g. recycle stability) For adequate production life:

  • Antioxidants
  • Light stabilisers
  • Flame Retardants

To survive end use:

  • Heat
  • Light
  • Ozone
  • Extraction
  • Etc.

BTC products for the rubber industry

BTC products for rubber processing

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Process stabilisation for Rubber

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Autocatalytical process Auto-oxidation

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Primary Antioxidants

(Free-Radical Scavengers)

  • Primary Antioxidants(Free-Radical Scavengers) -- Hindered Phenols
  • Free-radical scavengers react with chain-propagating radicals such as peroxy,

alkoxy, and hydroxy radicals in a chain terminating reaction.

  • The most widely used primary antioxidants are sterically hindered phenols. They are

very effective radical scavengers during both processing and long term thermal aging, and are generally non-discolouring.

  • Many also have received FDA approval.

O H O C O

4

IRGANOX 1010

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Author/BTC Month/Year CONFIDENTIAL Page 7

Primary Antioxidants – BHT type

Pro’s Low prices in the marketplace. Multi suppliers in the market. Concerns Patch testing performed under lab condition to patient in some cases has indicate that they have a contact allergy to BHT. Concerns about possible Carcinogenic effects

(Information from the Sciencelab.com)

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Secondary Antioxidants

(Peroxide Scavengers)

  • Peroxide scavengers (secondary antioxidants).
  • Decompose hydroperoxides (ROOH) into nonreactive products.
  • They are often used in combination with free radical scavengers (primary

antioxidants) to achieve a synergistic inhibition effect.

  • The most common secondary antioxidants are phosphites types.
  • Another class of secondary antioxidants are thioethers or organic sulfides.
  • Organic sulfides are very effective hydrogen peroxide decomposers
  • During long term thermal aging and are often used in combination with other

antioxidants like hindered phenols.

O P 3 IRGAFOS 168 P P O O O O O O IRGAFOS 126 O P OC2H5 2 IRGAFOS 38

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Author/BTC Month/Year CONFIDENTIAL Page 9

Secondary Antioxidants - Phosphite, Thioether

O P OC2H5 2 IRGAFOS 38

TNPP

Secondary Antioxidants Phosphite Thioether P OR' R OR'

R: OR' Ar R': Ar Alkyl

O P 3 IRGAFOS 168 P P O O O O O O IRGAFOS 126

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Author/BTC Month/Year CONFIDENTIAL Page 10

  • Primary antioxidant action
  • Secondary antioxidant action
  • Irganox 1520 L is a multifunctional liquid phenolic

antioxidant

  • Irganox 1520 L is non-staining, non-discoloring.
  • Low involatility, and stable to light and heat.
  • Good high temperature performance
  • Excellent processing stability
  • Good storage stability

OH SC H SC H CH

Irganox 1520L

Irganox 1520L

Dual Anti-oxidant: One Molecule – Two stabilisers

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 Approved for rubber articles in contact with food (BGVV: Empfehlung XXI, FDA: 177.2600)  Approved for HIPS (BgVV: Empfehlung VI + other European Countries, FDA: 177.1810 + 177.1640)  Other approvals granted (ex.: adhesives); FDA 175.105; 175.125  These approvals allow the use of IRGANOX 1520 for both tire grades and HIPS grades rubbers “ Antioxidant consolidation = cost savings”

Irganox 1520L-- Food Contact Approvals

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BTC products for the rubber industry

Process stabilisers by rubber type

  • Butadiene Rubber - BR
  • Ethylene propylene rubber - EPM/EPDM
  • Nitrile Butadiene Rubber – NBR
  • Butyl Rubber (isobutyl-co-isoprene) – IIR & CIIR/BIIR (Halobutyl

rubber)

  • Styrene Butadiene Rubber – SBR
  • Polyisoprene – IR
  • Neoprene - CR
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Processing Stabilisers for rubber

Recommendations for Butadiene Rubber (BR)

Cure Mechanism Heat Stabilisation Sulfur Cure Irganox 245; 1 phr Irganox 1035; 1 - 1.5 phr - best for BR Irganox 1520L; 1 phr (Food Contact Approvals) Irganox 5057; 1 phr - best for dynamic/anti-fatigue properties Peroxide Cure Non- Discolouring Irganox 1010 + PS 800/802 0.5+1 phr - best performance Irganox 1010; 0.5 - 1 phr Irganox 1076 + Irganox PS 800/802 0.5+ 1 phr - economical Irganox 1076; 0.5 - 1 phr - economical

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Stabilisation of High Cis (co-type) Polybutadiene

Influence of antioxidants

5 10 15 20 25 30 35 1 2 3 4 5 % Gel Fomation Weeks aging at 80°C

80°C aging: Gel formation

2 4 6 8 10 12 14 1 2 3 4 5 6 Yellowness index Weeks exposure

Discolouration of 2mm sheets during daylight exposure (weeks)

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Stabilisation of low cis Polybutadiene

Influence of AO on accelerated aging & gel sensitivity

15 30 45 60 75 90 5 10 15 20 25 30 unstabilzed 0.6% BHT 0.4% BHT +0.8% TNPP 0.2% Irganox 1520 0.1% Irganox 565 0.05% Irganox 565 + 0.5% TNPP Days aged at 80¸C until gel >2% Gel after Silicon oil aging (160°C, 20 mins) Gel after silicon oil ageing (160°C, 20min) Days aged at 80°C until gel content >2%

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Stabilisation of low cis Polybutadiene

Influence of AO on Brabender processing stability

5 10 15 20 25 30 35 40 45 Unstabilized 0.6% BHT 0.4% BHT +0.8% TNPP 0.2% Irganox 1520 0.1% Irganox 565 0.05% Irganox 565 + 0.5% TNPP

Brabender Induction time (minutes)

Longer Induction time indicates improved processing stability

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Processing Stabilisers for rubber

Recommendations for Ethylene Propylene Rubber (EPM/EPDM)

Cure Mechanism Heat Stabilisation Sulfur Cure Non-discolouring anti-oxidants

Irganox 1010 + Irganox PS 800/802 0.5 -1 +1 - 1.5 phr Irganox 1035; 1 - 2 phr

Peroxide Cure Non-discolouring anti-oxidants

Irganox 1010 + Irganox PS 800/802 0.3 - 0.7 +0.5 - 1 phr - long term stability Irganox 1010 + Irganox PS 800/802 0.5 -1 + 1 - 1.5 phr - high Temperature aging

Non-discolouring anti-oxidants

Irganox 1010 + Irganox PS 800/802 0.3 - 0.7 +0.5 - 1 phr - long term stability

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Processing Stabilisation of EPDM:

Mooney viscosity after 80°C oven aging.

45 50 55 60 65 70 10 20 30 40

mooney viscosity ML 1 + 4 (100) Weeks aging at 80°C

0.075% Irganox 1076 0.15% Irganox 1076 0.05% Irganox 1520 Unstabilised

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Processing Stabilisation of EPDM: Yellowness index after oven aging at 80°C

5 10 15 20 25 30 35 2 4 6 8 Yellowness index Weeks aging at 80°C 0.075% Irganox 1076 0.15% Irganox 1076 0.05% Irganox 1520 Unstabilised

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Processing Stabilisation of EPDM:

(Coagulated at pH 10): Mooney viscosity after 180°C hot mill test

40 45 50 55 60 65 70 75 80 85 90 1 2 3 mooney viscosity ML 1 + 4 (100)

Hours hot mill aging at 180°C

0.075% Irganox 1076 0.15% Irganox 1076 0.05% Irganox 1520 Unstabilised

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Light Stabilisation for the rubber industry

  • Photo-oxidation is initiated by the action of photons onto the rubber

article

  • Photo-oxidative degradation results from the combined action of light

and oxygen

  • The degradation process proceeds analogous to the auto-oxidation

cycle

= Photodegradation

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Light Stabilisation

  • Rubbers absorb UV-light due to their intrinsic chemical structure
  • If there is no light, there is no photo-degradation
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Light Stabilisation – Two main routes

  • UV Absorbers

Absorb harmful UV radiation and dissipation as heat Protect the polymer bulk; in thickness sections >0.1 mm (Lambert-Beer) Not effective at protecting surfaces or thin sections

  • Hindered Amine Light Stabilisers (HALS)

Scavenge radicals Activated during light exposure Protect bulk & surface Independent of article’s thickness Conventional HALS are deactivated by strong acid, NOR HALS are not.

  • Combination of HALS & UV absorber gives highest level of

protection.

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BTC products for the rubber industry

Light Stabilisation by rubber type

  • Diene Rubbers
  • Butadiene
  • Styrene Butadiene
  • Isoprene
  • Natural rubber
  • Ethylene propylene rubber - EPM/EPDM
  • Nitrile Butadiene Rubber – NBR
  • Butyl Rubber (isobutyl-co-isoprene) – IIR & CIIR/BIIR (Halobutyl

rubber)

  • Neoprene – CR, no light stabilisation recommendations
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Light stabilisers for rubber

Recommendations for Diene rubbers (BR, SBR, NR & IR)

Cure Mechanism Light Stabilisation Sulfur Cure UV absorber 1 -2 phr Tinuvin 234 Tinuvin 213 (liq) HALS 1 - 2 phr Flamestab NOR 116 - best performance (2 - 4 phr withour UVA) Tinuvin 123

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Light stabilisers for rubber

Recommendations for Diene rubbers (BR, SBR, NR & IR)

Cure Mechanism Light Stabilisation Peroxide Cure UV absorber dose 1 -2 phr Tinuvin 213 (liq) - best compatibility Tinuvin 571 (liq) - possible Tinuvin 326 or Tinuvin 234 - less volatile No need for HALS

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Light stabilisers for rubber

Recommendations for EPDM

Cure Mechanism Light Stabilisation Sulfur Cure UV absorber most important, 1 -2 phr alone or 1phr in blend with HALS Tinuvin 213 (liq) - best compatibility Tinuvin 571 (liq) - possible Tinuvin 326 or Tinuvin 234 - less volatile HALS max dose 1 phr only blended with UVA, higher

  • conc. maybe antagonistic with Sulfur used to cure

Tinuvin 123

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Light stabilisers for rubber

Recommendations for EPDM

Cure Mechanism Light Stabilisation Peroxide Cure UV absorber 1 phr Tinuvin 234 Tinuvin 213 (liq) HALS 1 - 2 phr Tinuvin 111 FDL Flamestab NOR 116 Tinuvin 770 DF

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Light stabilisers for rubber

Recommendations for NBR

Cure Mechanism Light Stabilisation Sulfur Cure UV absorber most important, 1 -2 phr alone or 1phr in blend with HALS Tinuvin 213 (liq) Tinuvin 571 (liq) Tinuvin 326 or Tinuvin 234 HALS max dose 1 phr only blended with UVA, higher

  • conc. Maybe antagonistic with Sulphur used to cure

Tinuvin 123 Tinuvin 111 FDL

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Light stabilisers for rubber

Recommendations for NBR

Cure Mechanism Light Stabilisation Peroxide Cure UV absorber 1 - 1.5 phr Tinuvin 213 (liq) - best compatibility Tinuvin 571 (liq) - possible Tinuvin 326 or Tinuvin 234 HALS 1 - 1.5 phr Tinuvin 111 FDL Flamestab NOR 116 Tinuvin 123

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Light stabilisers for rubber

Recommendations for IIR

Cure Mechanism Light Stabilisation Sulfur Cure UV absorber 1 phr Tinuvin 213 (liq) Tinuvin 234

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BTC products for the rubber industry

Other Products

  • Waxes
  • Luwax A
  • Luwax AL 3
  • Luwax AL 61 – reduces tack, especially in chlorinated rubbers.
  • NOP – for improving dispersion of Carbon black.
  • Koresin – tackifier –available via BASF.
  • Formic Acid – for processing of natural rubber.
  • Amines – for accelerant manufacture.
  • Pluriol – Used as mold release agents, lubricants, dispersant, vulcanisation

promoter & foam control. Also as a vulcanisation activator.

  • Modification of vulcanisation rate; modulus of elasticity
  • Reducing scorch time
  • Defoamers – waterbased foamaster or foamstar range, solvent based EFKA.
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BTC products for the rubber industry

Other Products

  • Plastisol – available from BTC in certain regions
  • Pluriol A can be used as a plasticiser for rubber, reactive PEG group could be

used as a copolymer in rubber formulations. The reactive groups are:

  • Ally - Pluriol A….R & Pluriol CA….211 M 43
  • Vinyl – Pluriol A…..V
  • Iosprenyl – Pluriol A……I
  • For the Emulsion production process anionic and non-ionic surfactants.
  • Tamol – Dispersion agent in rubber synthesis using emulsion process, particularly for

tire applications

  • Disponil
  • Pluronic
  • Lutensol
  • Crosslinking Co-agents: TMPTMA and Laromer TMPTA. Additives to improve

the peroxide and radiation crosslinking of rubber.

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End of presentation….

....Thank you for your attention

Thank You