New Keltan Grades for Flame Resistant EPDM Compounds€¦ · New Keltan Grades for Flame Resistant...

New Keltan Grades for Flame Resistant EPDM Compounds

Speaker: Philip Hough, Keltan M&S, TSADSGF Conference, Malmö 10th – 11th April 2013

Contents

Introduction

1.1 The move towards metal hydrates

1.2 The mechanism of metal hydrate flame retarders

1.3 Compounding with metal hydrates

2. EPDM Compounds

2.1 Keltan 1519R for improved physical properties

2.2 Keltan 0500R for improved processing

3. Conclusions

1. Introduction

The Kings Cross St Pancras fire of 1987 killed 31 people and injured another 60. Many of the deaths and injuries were caused by thick acrid smoke from halogen containing polymers. This tragedy led to London Underground introducing Fire Precautions Regulations (Section 12 Regulations) in 1989. This aimed to minimize the risks associated with the generation of noxious, corrosive fumes, and dense smoke from halogen containing products, including PVC cable insulation, and led to a general trend towards the use of “Zero Halogen Products” in enclosed public places.

This move towards non-halogen containing polymers created an opportunity for EPDM

However:

EPDM Burns!

1.1 Introduction – The move towards metal hydrates

For applications requiring flame resistance it is therefore necessary to develop compounds containing ingredients that;

�Give non-burning properties and/or

�Raise the temperature of ignition and/or

�Give self extinguishing properties

�Give fumes of low toxicity

�Reduce the spread of flames

�Have a low smoke density

1.1 Introduction – The move towards metal hydrates

Many traditional flame retardants are therefore excluded, e.g.

Material Objection

Brominated diphenyl esters/ethers Release of toxic and corrosive gas

Antimony oxide Contains heavy metal – toxic

Halogenated phosphorous products Release of toxic and corrosive gas

Halogenated paraffins Release of toxic and corrosive gas

Red phosphor Phosphine formation in contact with water

Therefore the use of metal hydrates becomes a logic al option

Contents

Introduction




2. EPDM Compounds



3. Conclusions

1.2 Metal Hydrate – Mechanism of Flame Retardation

Use of metal hydrates

Aluminium trihydrate (ATH):

Magnesium dihydrate:

> 200°°°°C

2 Al(OH)3 Al 2O3 + 3 H2O

1051 J/g

> 340°°°°C

Mg(OH)2 MgO + H2O

1316 J/gData Source: ALBERMARLE

1.2 Metal Hydrate – Mechanism of Flame Retardation

� Endothermic reaction from water emission

� Dilution of flammable gases due to formation of water vapour

� Moisture shroud reduces oxygen availability

� Formation of protective char leading to;

�Thermal insulation

�Adsorption of smoke particles

� Reduced % of polymer in compound

Reference: EFRA

Data Source: ALBERMARLE

Contents

Introduction




2. EPDM Compounds



3. Conclusions

1.3 Compounding of EPDM with Metal Hydrates

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-0.8

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Rel

ativ

e E

ffect

on

LOI

ATH Mg(OH)2 Clay Whiting Par. Oil Ester Oil

Ingredient

Relative Effect of Filler and Plasticizer on Limiti ng Oxygen Index (LOI) Value of an EPDM Compound

� Zinc Borate also considered to give a synergistic improvement in combination with ATH and Mg(OH)2

� Calcium carbonate, silica, silicates and sulphates also give some flame retardant benefit, probably due to dilution of combustible material, i.e. the polymer


General Rules

To achieve a reasonable level of flame resistance (LOI > 30) AT LEAST50 wt% of the compound should be metal hydrate

Zinc borate has been found to give synergistic improvements when used in combination with hydrated fillers

Paraffinic processing oil reduces LOI, and should only be used <15phr

Phosphate and ester plasticizers have less effect on LOI, but have limited compatibility with EPDM; use at levels of < 15phr


Disadvantages of using metal hydrates for flame res istant EPDM

Metal hydrates act as diluent fillers, having no reinforcing properties. High loadings cause a reduction of physical properties

High filling levels coupled with low oil addition result in high viscosity compounds that are difficult to process

Keltan Solutions

Keltan® 1519R MAH grafted EPM for polymer / filler coupling

Keltan® 0500R Very low viscosity EPM for improved processing

Contents

Introduction




2. EPDM Compounds



3. Conclusions

2.EPDM Compounds2.1 Keltan 1519R For Improved Physical Properties

Property Unit Typical Value Test Method

Polymer type Copolymer

Ethylene content Wt% 49 ASTM D 3900

Grafted Maleic Anhydride Wt% 1.9 FT-IR

Molecular weight distribution Narrow GPC

Mooney Viscosity ML(1+4) 125°C

MU 65 ISO 289

Melt flow Index 190°C/2.16kg g/10 min 4.5 ASTM D1238

Product DescriptionLow molecular weight amorphous copolymer grafted with 1.9 wt% maleic anhydride produced by reactive extrusion technology

2.1 Keltan 1519R For Improved Physical Properties – High ATH Filled Compound

Increased Mooney due to;

� MA cluster formation

� Improved polymer / filler interaction

KELTAN 5470 25 20KELTAN 2650 75 70Keltan 1519R 10Carbon black N-550 50 50Whiting 50 50ATH 200 200Paraffinic oil 15 15DOA 15 15ZnO 5 5Stearic acid 1 1TEA 1 1Rhenogran® CaO-80 6 6Rhenogran® CBS-80 1 1Rhenogran® TMTD-80 1 1Rhenogran® ZDBC-80 2.5 2.5Rhenogran® S-80 2.5 2.5

Total phr 450 450

Keltan 1519 - 0phr Keltan 1519 - 10phr Mooney ML (1+4) @ 100°C ISO 289Keltan 1519 - 0phr Keltan 1519 - 10phr

Initial [MU] 71 119ML [MU] 51 81

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2.1 Keltan 1519R For Improved Physical Properties – Improved Tensile Properties

0phr Keltan 1519R / 200phr ATH 10phr Keltan 1519R / 200phr ATH

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2.1 Keltan 1519R For Improved Physical Properties– Improved Tensile Properties

The addition of Keltan 1519R gives:

�Dramatic increase of stress load at low strain levels

�Higher ultimate tensile strength

�No loss of final elongation

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2.1 Comparison of Tensile Strength for ATH, Mg(OH) 2 and Clay in Peroxide Cured W&C Compound

Tensile strength/Keltan 1519R content

0

2

4

6

8

10

12

14

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0 5 10 15 20

Keltan 1519R (Phr)

Ten

sile

str

engt

h (M

Pa)

ATH

Clay

MgOH

� Fillers used at 150phr

� Martinal OL-107C � ATH Surface modified aluminum hydroxide

� Clay Burgess � Surface modified calcined aluminum silicate

� Magnifin H10A � Magnesium hydroxide vinyl silane coated

� Total compound = 361phr

Tensile strength improves for ATH and Mg(OH)2, but not effective for Clay

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Contents

Introduction1.1 The move towards metal hydrates



2. EPDM Compounds2.1 Keltan 1519R for improved physical properties


3. Conclusions

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2.2 Keltan 0500R for Better ProcessingPolymer Properties

Product DescriptionAmorphous ethylene/propylene copolymer with very low Mooney viscosity produced via a down shearing process. This grade can be used as a polymeric plasticizer in low-oil or oil-free EPDM based compounds to give improved processability

Property Unit Nominal Value Test Method

Ethylene Content wt% 49 + 2.1 ASTM D3900

Melt Flow Index 2.16kg / 190°C g / 10 min 11 + 3 ASTM D1238

Volatile Matter wt% < 0.5 ISO 248/ASTM D5668

2.2 Keltan 0500R for Better Processing – Handles Like Rubber

� Unlike other plasticizers, bales can be unpacked, cut,

mixed and conveyed like regular Rubber bales

� Managing the cold flow:

� Exhibits cold flow behavior

� Packaging consists of individual, non-leaking, easy release

boxes

� Upright storage of boxes is required

� Remainder of bales can easily be stored in original boxes

0 hours

24 hours

2.2 Keltan 0500R for Better Processing – Low Oil Belt Compound

� Finding the balance between processing and compound performance for oil free applications

Successively replace K6160D by ultra low viscosity K0500R as polymeric plasticizer

The low molecular weight polymer facilitates processing under shear conditions

The high molecular weight polymer helps to maintain mechanical properties

Keltan 6160D 100 90 80 70 60 50Keltan 0500R 10 20 30 40 50CB N650 100 100 100 100 100 100Paraffinic Oil 15 15 15 15 15 15Paraffin Wax 3 3 3 3 3 3Zinc Oxide 5 5 5 5 5 5tackifying Resin 5 5 5 5 5 5Zinc Stearate 3 3 3 3 3 3Perkadox 14-40 7 7 7 7 7 7Coagent 4 4 4 4 4 4Total phr 242 242 242 242 242 242

70/30 60/40 50/50K6160D/K0500R 100/0 90/10 80/20

2.2 Keltan 0500R for Better Processing – Broadening of Molecular Weight Distribution

0

0.2

0.4

0.6

0.8

1

1.2

3 3.5 4 4.5 5 5.5 6 6.5 7

log MW

K740

K1200A

50/50 blend

K6160D

K0500R

0

10

20

30

40

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60

70

80

90

100

110

120

130

140

150

K740 pure 90/10phr 80/20phr 70/30phr 60/40phr 50/50phr

0

50

100

150

200

250

300

T.S. [MPa] Hardness [°Sh.A] Tear str. Delft [N] Elonga tion [%] ML

0

10

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90

100

110

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130

140

150


0

50

100

150

200

250

300

T.S. [MPa] Hardness [°Sh.A] Tear str. Delft [N] Elongation [%] ML

2.2 Keltan 0500R for Better Processing – Conclusion: Strongly reduced ML while maintaining similar physical properties

0

10

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0

50

100

150

200

250

300


K6160D pure

2.2 Keltan 0500R for Better Processing – Conclusion: Strongly reduced ML with only a small loss of elasticity (may be compensated by small peroxide increase)

0

10

20

30

40

50

60

70

K740 10phr 20phr 30phr 40phr 50phr

0

20

40

60

80

100

120

140

160

Comp. Set 23 °C [%] Comp. Set 100 °C [%] Comp. Set 150 °C [%] ML

K6160D pure

2.2 Keltan 0500R for Better Processing – Application Recipe; HFFR Cable Compound

100/0 85/15K2470L 100 85K0500R 15N539 25 25DIDP 10 10ZnO 5 5Stearic acid 1 1Cao-80 7 7ATH (Martinal OL-107C) 160 160Perkadox 14-40 MB 5 5

TAC-70 1.5 1.5

Total phr 314.5 314.5

Burn Testing UL-94 Vertical test100/0 85/15

Rating V2 V2Note; No drip/deposit of test pieces was observed

Test Results 100/0 85/15

1) Rheological propertiesML1+4 @ 100°C [MU] 78 63MDR at 180°CT2 [min] 0.5 0.5T90 [min] 6.4 6.1MH-ML [dNm] 36 30

Garvey Die rating 3/3/3/3 3/4/4/4

Vulcanised properties Cure 12min. 180°C100% Mod. [MPa] 2.8 2.5T.S. [MPa] 9.1 8.2E.B. [%] 230 225Hardness [ShA] 77 76

Comp.set [%] 22hr.70°C 14.6 14.0

Contents

Introduction




2. EPDM Compounds



3. Conclusions

3. Conclusions

A general trend towards the use of zero halogen products in enclosed public places has necessitated the use of non-halogen containing polymers in combination with metal hydrate fillers.

To be effective as flame retarders, metal hydrate fillers must be used at levels of at least 50 wt% in compounds containing low levels of processing oil. This adversely effects both the processing and cured physical properties of the compound.

Lanxess Keltan Elastomers offers innovative products that improve both processing and physical properties of high filled, low oil EP(D)M based compounds;

� Keltan 1519R gives coupling between metal hydrate f illers and EP(D)M polymer to improve physical properties

� Keltan 0500R reduces compound viscosity for improve d process flow, with a minimum effect on physical properties

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Disclaimer

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Thank You for Your Attention

New Keltan Grades for Flame Resistant EPDM Compounds€¦ · New Keltan Grades for Flame Resistant...

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