Mitsui Metallocene EPT - pn-pnic.compn-pnic.com/pdf/Meta.pdf · Mitsui Metallocene EPT shows excellent filler dispersion. Compound with 1% CB Roll Mill CB EPT Other’s EPDM Mitsui

Mitsui Metallocene EPT


Mitsui Chemicals, Inc.

Ｃｏｎｔｅｎｔｓ

1. Advantages of Mitsui Metallocene EPDM

2. Mitsui EPT for Automotive Parts

Grade Lineup of Mitsui Metallocene EPT

Tire Inner Tube, Roofing Sheet－－1.749.2402060M

Molding－－7.644.5454045M

Anti-Vibration Rubber, Gasket, Grommet－405.464.0513072EM

－

10

20

10

－

Oil(phr)

－

－

－

20

－

PE (phr)

4.6

5.2

4.5

5.0

7.6

ENB(wt%)

Glass Run ChannelDoor Opening Trim56.436（150℃）PX-049PEM

Hose47.5593090EM

Hose, Grommet, Gasket64.5433062EM

Hoses, Grommets, Gaskets,Extrusion Applications65.9613092M

Corner Joint Sponge53.58（100℃）X-4010M

ApplicationsEthylene

(wt%)Moony ViscosityML1+4（125℃）

Grade

※ These values are typical properties only and are not to be regarded as sales specifications.

Advantages of Metallocene EPT

Synthetic Extender Oil

Long Lifetime

Excellent Extrudability

Excellent MixingProcessability Disentangled Molecules

Low Chlorine Content

Narrow MWDNarrow Diene DistributionHigh Mechanical Property

No Deashing ProcessLess Gel



Long Lifetime






Long Life by Low Chlorine Content

Mitsui Metallocene EPT has longer lifetimeby lower chlorine content.

MetalloceneEPT

Chl

orin

e C

onte

nt (p

pm)

ConventionalEPT

0

50

100Chlorine accelerates discoloration and degradation

Degradation of Copper by Chlorine

Metallocene EPT Conventional EPT

Copper PlateEPT

After 120ºC×2weeks

Chlorine accelerates the corrosion of copper.

Degradation of Nylon by Chlorine

Metallocene EPT Conventional EPT

Nylon PlateEPT

After 120ºC×2weeks

Chlorine accelerates the degradation of Nylon.



Long Lifetime






Excellent Mixing Processability

Molecules of Mitsui EPT are disentangled by extruder.

Extruder

EPDM

Other’s Production Process(Steam Stripping)

EPDM

DenseEntangled

Disentangled Molecules

Polymerization in Solution Mitsui


Mitsui Metallocene EPT shows excellent filler dispersion.

Compound with 1% CB

Roll Mill

EPTCBOther’s EPDM

Mitsui EPT

CB Dispersion Test

3min,60℃


Compound’sState

Mixing Chart

OthersMitsui EPT

2min1min

Total 3min Total 4min

Mixing time can be decreased with Mitsui EPT



Long Lifetime






Comparison between Synthetic Oil and Paraffinic Oil

0.880.88Density

Narrow(by Metallocene Catalyst)

BroadMWD

Liquid EPRParaffin HydrocarbonComponent

Purity100% Ethylene Propylene

RubberMixture of Hydrocarbon

Mitsui’s Synthetic OilParaffinic Oil

Mitsui’s synthetic oil is liquid EPR synthesized by Metallocene catalyst

Why Synthetic Oil in Mitsui Metallocene EPT?

Synthetic oil (Liquid EPR) has better properties

1. Good compatibility to EPDM(Component is same as EPDM)

2. High purity

3. Less low molecular weight component(Prevention of oil vaporization)

4. Stability of viscosity at low temperature

Stable Viscosity of Synthetic Oil

Temperature [ºC]

Vis

cosi

ty [P

a·s]

Paraffinic Oil

Synthetic Oil

Excellent Extrudability by Synthetic Extender Oil

Synthetic oil extended in Mitsui Metallocene EPTshows excellent extrudability.

Hardness

purity

Processability

Low TemperatureProperty

Bleeding

Volatility

Synthetic Oil

Extrusion test

ParaffinicOil

Paraffinic Oil

Synthetic Oil

Comparison of Properties




Long Lifetime






Less Gel by Metallocene Catalyst

Metallocene process doesn’t need deashing

Deashingby industrial water Oxygen

MCIMetallocene

Process

＜ Extruder ＞

No deashingReactor

OthersVanadiumProcess

Steam stripping

Reactor

Gelation

No Gelation

Effect of Oxygen on Gelation

0 0 0

1.3

1.8

4.44.8

0

1

2

3

4

5

6

1 10 100 1000

High

Low

Concentration of Oxygen (10-3 mmol/P-Kg)

Gel

Per

cent

age

(%)

250ºC×1day Heated

Experiment

Oxygen accelerates gelation.

Amount of Gel in Polymer

OthersVanadium process

MitsuiMetallocene process

Polymer is dissolvedin decane at 150 ℃for 4 hours.

Polymer

Solvent(decane)

Net

Dec

ane

GelMitsui EPT doesn’t have any gel.

Quality Improvement by Less Gel

Others; Vanadium process

MCI; Metallocene process

Extruded

Extruded



Long Lifetime






Cost Saving by High Loading

Mw/Mn=2.2

Metallocene EPDMMetallocene EPDM

500phrCompound

¥28/LCost Saving

Mw/Mn=2.8Broad Diene Distribution Narrow Diene Distribution

Conventional EPDMConventional EPDM

16Compression Set, %

360Elongation, %

9.8Tensile Strength, MPa

Conventional EPDM

17Compression Set, %

340Elongation, %

9.4Tensile Strength, MPa

Metallocene EPDM

Cost saving is possible by high loading with Metallocene EPT.

(330phr Compound)



Long Lifetime






Agenda

1. Advantages of Mitsui Metallocene EPDM

2. Mitsui EPT for Automotive Parts

Mitsui Metallocene EPT for Automotive Parts

2. Corner joint1. GRC

4. Hose 3. W/S sponge

PX-049PEM

3090EM

X-4010M

8120EM

Mitsui Eptalloy

3092M

8110M

5. Raw material of TPV

3072EPM

3062EM3092(P)M

3092(P)M


Mitsui Metallocene EPTfor Glass Run Channel

PX-049PEM, 3092M


Mitsui Metallocene EPT for Glass Run Channel

Glass

♦♦ Sealing performanceSealing performance♦♦ Appearance :Appearance : Smooth surface, no obstacles, no bloomingSmooth surface, no obstacles, no blooming♦♦ DurabilityDurability

Glass Run Channel (GRC)

・Wetherseal between Grass and Door・Absorption of Glass Vibration

Requirements

Properties of PX-049PEM

PX-049PE is a EPDM / PE alloy in which PE is very homogeneouslydispersed by Mitsui’s unique production process.

MicrophotographEPDM

ＰＥ

Low specific gravityEasy production of harder productsLess defective articlesHigh load formulationFaster extrusion speed & Smooth surface by high fluidity

Features of PX-049PEM

PX-049PEM

10phrExtended Oil

36ML(1+4)150℃

5wt%ENB content

20phr

56wt%

Polyethylene content

Ethylene content

Specific Gravity of Weather Seal Materials

Weight Saving of Rubber Products

1.30.91.3S.G.

EPDMTPVPVCMaterials

Customer’s RequirementWeight Saving

Eptalloy (EPT/PE)

Door Opening Trim

Weight Saving by Eptalloy

1.3

EPDM

1.20.91.3S.G.

EptalloyTPVPVCMaterials

Sight Foaming

0.9-1.0S.G. 0.95

1

2

3

4

5

1

2

3

4

5

Non-melt PE

PX-049PEConventional EPDM

etc.

Number of Foreign Materials(1/100m)

Rate of Defects : 0.7％

0 2 4 6 8 10

Caused by

White Filler

Carbon Black

Rubber

Advantage of Eptalloy for Defect Rate

Rate of Defects : 5.0％

Number of Foreign Materials(1/100m)0 2 4 6 8 10

PX-049PEM Formulation for GRC

421 phrA-Compound Total

1.2753.611.2440

-

13051

160853010

Solid

＜Properties of GRC product＞Specific gravityHardness (HA)M100 (MPa)TB (MPa)EB (%)

Foaming agent

＜Formulation＞Mitsui Eptalloy PX-049PEMZinc OxideStearic acidFEF Carbon BlackParaffinic OilGround Calcium CarbonateCalcium Oxide

421 phr

1.0682.87.8370

OBSH 0.3phr

13051

160853010

Foaming

Slight Foaming

Sectional profile

Acc.MBT(1.5)/ZnBDC(2.0)/EU(1)/TMTD(0.3)/DTDM(0.5)/Sulfur(1.5)

Properties of 3092PM

3092PM is non oil-extended EPDM with high Mooney viscosity which is suitable for extruded products and molded.

High load formulationHigh mechanical strengthExcellent extrudability and moldability

Features of 3092PM

3092PM

-phrExtended Oil

61ML(1+4)125℃

4.6wt%ENB content

66wt%Ethylene content

3092PM Formulation for GRC

Formulation Mitsui EPT 3092PM 100 100Zinc Oxide 5 5Stearic Acid 1 1SRF Carbon Black (N774) 164 157Paraffinic Oil (Sunpar2280) 106 83Ground Calcium Carbonate 30 30Calcium Oxide 6 6

A-Compound Total 412 382Accelerator

MDB 0.5 0.5ZnBDC 1.0 1.0EU 1.0 1.0TBTD 0.5 0.5

Sulfur 1.0 1.0Final-Compund Total 416 386

<Vulcanizate Properties>Hardness (HA) 71 75TB (MPa) 11.9 13.4EB (%) 400 340


Mitsui Metallocene EPTfor Corner Joint

X-4010M


Mitsui Metallocene EPT for Corner Joint

Corner Joint

Corner Joint

♦♦ Sealing performanceSealing performance♦♦ Appearance :Appearance : Smooth surface, no obstacles, no bloomingSmooth surface, no obstacles, no blooming♦♦ DurabilityDurability

Requirements

X-4010M for Corner Joint

X-4010M has excellent fluidity with ultra-low Mooney viscosity,and high vulcanization speed with high ENB content.

< Ultra Low Moony Grade >

Excellent transfer and injection processabilitySuitable for corner joints of weather strip spongeGood modifier for high viscosity EPDM

Features of X-4010M

X-4010M

-phrExtended Oil

8ML(1+4)100℃

8wt%ENB content

59wt%Ethylene content

Excellent Fluidity of X-4010M

Length (cm) 20 25

Mitsui EPTX-4010M

ML 8

Competitor’sML 35

Mitsui X-4010M shows excellent fluidity

X-4010M Formulation for Solid Corner Joint

Hardness65 Hardness70

100 1005 51 1

75 8520 2020 200.5 0.50.3 0.30.8 0.84.0 4.0

Minimum Viscosity Vm145ºC 13 18t5 (145ºC) min 4.3 4.2Tc90 (180ºC) min 3.0 3.1

Tensile Strength MPa 10.8 11.9Elongation at Break % 430 420Hardness (Shore A) - 66 73Compression Set (70ºC, 22h) % 18 17

Unvulcanized Properties

Vulcanized Properties (170ºC × 15min cured, CS: 20min cured)

MBT

Calcium Oxide

ZnBDCSulfur

Paraffinic OilGround Calcium Carbonate

Formulation

Mitsui EPT X-4010MZinc OxideStearic AcidSRF Carbon Black

X-4010M Formulation for Sponge Corner Joint

704251

72600.51.5

TETD 0.5TMTD 0.5

1.0ADCA/DPT (Eiwa Chemical, S-537) 10

0.5

Minimum Viscosity Vm100ºC 12t5 (145ºC) min 12.7Tc90 (180ºC) min 2.9

Specific Gravity - 0.63Tensile Strength MPa 3.3Elongation at Break % 420Compression Set (70ºC, 22h) % 16

Paraffinic Oil

Formulation

Mitsui EPT X-4010M

Zinc OxideStearic AcidSRF Carbon Black

Mitsui EPT 3072EM

Unvulcanized Properties

Vulcanized Properties (Sponge Properties)

MBT

Calcium Oxide

ZnBDC

Sulfur


Mitsui Metallocene EPTfor W/S Sponge

8120EM, 8110M


Mitsui Metallocene EPT for W/S Sponge

♦♦ Noise Noise IInsulationnsulation♦♦ Sealing PerformanceSealing Performance♦♦ Appearance : Appearance : Smooth surface, no obstacles, no bloomingSmooth surface, no obstacles, no blooming

Weatherstrip Sponge

・Wetherseal between Body and Door・Absorbing Shock of Shutting Door

Requirements

W/S sponge

Door

Body

8120EM and 8110M for W/S Sponge

8120EM and 8110M have excellent shape retention with branching structure. These grades are suitable for sponges.

Excellent shape retentionExcellent compression setHigh load formulationSmooth surface

Features of 8120EM and 8110M

8120EM, 8110M

8110M8120EM

20

11.6

42.6

65

-phrExtended Oil

62ML(1+4)150℃

10.9wt%ENB content

40.9wt%Ethylene content

Excellent Shape Retention

HAV: 250 ℃, 1 min

8120EM8110M8120EM8110M

ConventionalConventional

Excellent Shape Retention during Vulcanization

Branched Structure

lCH2 CHCH

CH2 CHCH

CH2

CH CHm

VNB

ENB

CH 2 CHCH 2CH 2

CH 3

m n l

VNB : Vinyl Norbornene

Viscoelasticity of 8120EM and 8110M

1.0.E+03

1.0.E+04

1.0.E+05

1.0.E+06

1.0.E+07

1.0.E+08

0.001 0.01 0.1 1 10 100 1000Frequency [rad/s]

η* [P

a·s]

Good shape retentionby higher viscosity

Mitsui EPT 8120EM, 8110M

Conventional EPDM(Wide MWD)

Conventional EPDM(Narrow MWD)

Good processabilityby lower viscosity

Good shape keeping and processability

Door Sponge Formulation

Formulation 8120EM 120 120 -8110M - - 100Zinc Oxide 5 5 5Stearic Acid 2 2 2SRF Carbon Black (Cabot SP5000A) 100 - 100SRF Carbon Black (N774) - 85 -FEF Carbon Black (N550) - 20 -Paraffinic Oil 75 70 95Ground Calcium Carbonate 50 50 50Calcium Oxide 2 2 2

A-Compound Total 354 354 354Specific Gravity 1.17 1.18 1.18

OBSH (NEOCELLBORN N#1000SW) 3.5 3.5 3.5Final-Compund Total 364.4 364.4 364.4

<Vulcanizate Properties>Specific Gravity 0.60 0.58 0.55TB (MPa) 2.6 2.5 2.4EB (%) 270 260 250

Acc.MBT(2.0)/DPTT(1.0)/ZnEDC(1.1)/CBS(1.0)/TeEDC(0.3)/Sulfur(1.5)/

SSM Sponge Formulation

Formulation 8120EM 120 120 -8110M - - 100Zinc Oxide 5 5 5Stearic Acid 2 2 2SRF Carbon Black (Cabot SP5000A) 100 - 100SRF Carbon Black (N774) - 85 -FEF Carbon Black (N550) - 20 -Paraffinic Oil 75 70 95Ground Calcium Carbonate 50 50 50Calcium Oxide 2 2 2

A-Compound Total 354 354 354Specific Gravity 1.17 1.18 1.18

OBSH (NEOCELLBORN N#1000SW) 1.5 1.5 1.5Final-Compund Total 362.4 362.4 362.4

<Vulcanizate Properties>Specific Gravity 0.67 0.68 0.66TB (MPa) 3.0 3.1 2.9EB (%) 400 420 400

Acc.MBT(2.0)/DPTT(1.0)/ZnEDC(1.1)/CBS(1.0)/TeEDC(0.3)/Sulfur(1.5)/


Mitsui Metallocene EPTfor Automotive Water Hoses

3090EM, 3062EM, 3092M


Mitsui Metallocene EPT for Water Hoses

♦♦ Low Temperature PropertiesLow Temperature Properties♦♦ Heat ResistanceHeat Resistance♦♦ ExtrudabilityExtrudability♦♦ Long life timeLong life time

Automotive Water Hoses

Requirements

3090EM for Automotive Water Hoses

3090EM has excellent mixing processability and extrudability with synthetic extender oil. Excellent low temperature properties of 3090EM is suitable for automotive water hoses.

Excellent low temperature propertiesExcellent mixing processabilityExcellent extrudability

Features of 3090EM

3090EM

10phrExtended Oil

59ML(1+4)125℃

4.7wt%ENB content48wt%Ethylene content

3090EM Formulation for Water HosesFormulation

Mitsui EPT 3090EM 110 77Mitsui EPT 3092PM 30Zinc Oxide 5 5Stearic Acid 1 1FEF Carbon Black （N550） 130 130Ground Calcium Carbonate 30 30Paraffinic Oil 65 68Polyethylene glycol (PEG#4000) 1 1Calcium Oxide 7.0 7.0

A-compound Total 349 349Accelerator

CBS 0.5 0.5ZnBDC 1.5 1.5EU 0.5 0.5TMTD 0.5 0.5

Dithiodimorpholine 1.5 1.5Sulfur 0.3 0.3Unvulcanization Properties

Vm（125C） °C 47.0 52.0 ｔ5（125℃） min 10.1 9.8 TC90 (160℃) min 6.1 6.1

Vulcanizate Properties 15min Cured at 160°CHardness (Shore A) 69 69Tensile Strength (MPa) 11.1 13.1Elongation at Break (%) 520 530Compression set / 22h at 70°C （20min Cured） 26 24

Thank you for your attention.

Documents

Mitsui Metallocene EPT - pn-pnic.compn-pnic.com/pdf/Meta.pdf · Mitsui Metallocene EPT shows excellent filler dispersion. Compound with 1% CB Roll Mill CB EPT Other’s EPDM Mitsui