Mitsubishi International Corporation - micchem.com · Mitsubishi International Corporation 2 Classification of Diene Rubber Polybutadiene (BR) High Cis BR Butadiene Rubber Styrene-Butadiene

1

Synthetic Rubber

For HIPS, MBS and Mass-ABS

Mitsubishi International Corporation

2Mitsubishi International Corporation

Classification of Diene RubberHigh Cis BRPolybutadiene (BR)

Butadiene Rubber Styrene-Butadiene Copolymer (SBR)

Styrene-Butadiene-Styrene block Copolymer (SBS:Thermoplastic Elastomer)Hydrogenated SBS-SEBS

Low Cis BR

Natural Rubber (NR)

Polyisoprene (IR)

High Trans BRHigh Vinyl BR

Emulsion-SBR

Solution-SBR

Isoprene Rubber


Characteristics of Solution Polymerization Technique

Molecular Weight Controllable by ratio between Feed Monomer/Catalyst because of living anionic polymerizationMWD (Mw/Mn) Narrow due to living anionic polymerization. Changeable according to polymerization

conditions and reactionsBranch Little during polymerization. Easily controlled by adding coupling agent

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H2CHC C

HCH2

CH2

HC

CH2

HC C

H

H2CR C

H2

HC C

HCH2

Li- +

CH2

HC C

H

H2CRH2C CH C

H2CH Li +-

R-Li

+

Contr

ol of

Macr

o-

stru

cture

Butadiene

Styrene

Polybutadiene (BR)

Styrene-butadiene copolymer (SBR)

Catalyst Terminator Stabilizer

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Microstructure 1,4-Cis; 1,4-Trans; 1,2-Vinylpolybutadiene parts) Vinyl content easily controlled by adding modifier (polar compounds)

Bound Styrene Content Easily controlled by butadiene/styrene feed ratioBlock Styrene Content Random, block, tapered Controlled by polymerizations conditionsHydrogenated (Bd) 1,2-Vinly….Butylene 1,4-Cis Trans….Ethylene

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ol of

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Mic

rst

ruct

ure


Relationship between Low Cis, High Cis Rubber

Broad MWD (Mw/Mn 3), Much branchingMicrostructure: Cis 96%, Vinyl 4%Tg: -105 degrees C Tm: 10 degrees CNo copolymerization of styrene

Coordinate polymerization(Solution)Ni catalystCo-Al catalyst

High Cis Rubber

Broad MWD, Much branchingMicrostructure: Cis 12%, Trans 70%, Vinyl 18%Control of polymer structure Little variation-- Styrene content-- Molecular weight

Radical polymerization(Emulsion)Potassium peroxodisulfate

MWD narrow, Little branchingMicrostructure: Cis 35%, Trans 52%, Vinyl 13%Tg: -98 degree C Tm: nilControl of polymer structure Large variation-- Vinyl content-- Block SBR, Random SBR-- Coupling reaction, Terminal modification, etc.

Anionic polymerization(Solution)Rli catalyst

Low Cis Rubber

Polymer StructurePolymerization


Microstructure of Polybutadiene

Nil(NIL)

-7 ° C •VinylBond

Tm (Crystallization)Tg (Elasticity)

Nil(NIL)

100 ° C •Styrene

50∼100°(YES)

-100 ° CTransBond

-10 ∼0 ° C

(YES)

-110 ° C CisBond

HomopolymerTg , Tm

Polymer structure

CH2

HC CH

H2C

CH2

HC

HC CH2

CH2

HC

CH2

HC CH

H2C


Microstructure of Polybutadiene (2)

○15 ~ 2060 ~ 8010 ~ 20Radical• K2S2O4

○~ 70~ 50~30RLi / Polar solvent

VinylTransCis

×1 ~ 21 ~ 296 ~ 98Co• Co(Octanate)2• AlR2Cl• H2O

×1 ~ 21 ~ 296 ~ 98Ni• Ni(Naphtanate)• AlR3• BF3•(C2H5)2

○135235RLi

StyreneCopolymerizable

Microstructure (%)Catalyst

○ = Copolymerizable with styrene× = Not copolymerizable with styrene


Comparison of Batch Polymerized Rubber with Continuous Polymerized Rubber:Molecular weight Distribution

0

10

20

30

40

50

60

70

80

90

100

12

Frac

tion

(%)

Continuous PolymerizationAsadene 5 5 A EMw/Mn=2.2

Batch polymerizationAsaprene 730AXMw/Mn=1.2

High Cis RubberMw/Mn=3.5

13 14 15 16 17 18 19

High Molecular Weight Low Molecular WeightRetention Time (min)


Synthetic Rubber for HIPS Use

Acquired CharacteristicsAbility to crosslink/Graft during HIPS polymerizationStyrene insolubles (gel) Extremely lowImpurity Extremely lowColorlessHandling Improved cold flow


Synthetic Rubber for HIPS Use

Commercial Rubber for HIPS UsePolybutadiene rubber: Low Cis BR, High Cis BR

• Comparison of Low Cis BR with High Cis BR as rubber for HIPS:

Styrene-butadiene copolymer• Random SBR

• Block SBR• Special grade: Super high gloss HIPS, Transparent

HIPS, etc.

Low reactivityLow reactivityHigh Cis Br

High reactivityHigh reactivityLow Cis BR

CrosslinkingGraft


Synthetic Rubber for HIPS (Mass-ABS)

Transparent14513520-35Asaprene625A

SBR

Thermal Stability

Partially hydrogenated BR

750H300APH-BR

VINYL L

TRANS SCIS

High GlossMass-ABS14513510-15

Asaprene610A

18493335470Asaprene730AX

13523585330Asadene35AE

Super High Gloss14513534-39Asaprene670A

High Impact18493377550Asaprene760AXLow Modulus

High Gloss18493325400

Asaprene720AX

Low SV

General purpose

135235170500Asadene55AE

General

Microstructure (%)SV(CPS)MLStyrene

(%)Grade


Relationship between Mooney and Solution Viscosities

1

10

100

1000

10 20 30 40 50 60 70 80

55AE

760AX

35AE

High Cis

730AX

720AX

So

luti

on

Vis

cosi

ty [

5w

t% i

n S

tyre

ne]

Difference

by couplingin branch

Mooney Viscosity [ML1+4, 100°C]


720AX

35AE

55AE

730AX

760AX

Cold Flow of Asaprene, Asadene, Other Rubbers

Rubber Ht.

1 Kg.

Sample size (mm):LXWXH=40X40X50

Cold flow %) = HO —HtHO X 100

HO=Initial height of sample

Ht= Height of sample after t min.

Co

ld F

low

%)

80

70

60

50

40

30

20

10

00 20 40 60 80 100 120

Time (min.)


Relationship between Solution Viscosity and Rubber Particle Size (Using Polybutadiene rubber)

0.0

1.0

2.0

3.0

4.0

5.0

6.0

0 50 100 150 200

730AX

35AE

55AE

35AE

730AX

55AE

Agitation speed: 25 rpm

Agitation speed: 75 rpm

•1.5L Glass bottle•Rubber/SM = 595 (wt%)

R.P

.S.

(µm

)

Solution viscosity (cps)


0

10

20

30

40

12 13 14 15 16 17 18 19

Molecular Distribution of Weight for Asadene 55AE/35AE

Asadene 35AE

Asadene 55AE

High molecular weight Low molecular weightRetention time (min.)

Fra

ctio

n (

%)

70

60

50

20


0

100

90

80

70

60

50

40

30

20

10

Asaprene 730AX

Asaprene 760AX

Fra

ctio

n (

%)

Distribution of Molecular Weight in Asaprene Series

12 13 14 15 16 17 18 19 20

lecular weight Low molecular weightRetention time (min.)

High mo


Relationship between Rubber Particle Size and Izod, Gloss (Using polybutadiene rubber)

0

2

4

6

8

10

12

14

16

0

10

20

30

40

50

60

70

80

90

100

0.4 0.8

Izo

d im

pact

(kg

•cm

/cm

)

Glo

ss (

%)

Asaprene Series 720AX, 730AX

Asadene Series 55Ae, 35AE

Asaprene Series 720AX, 730AX

Asadene Series 55AE, 35AE

1.2 1.6 2 2.4 2.8 3.20.4 0.8 1.2 1.6 2 2.4 2.8 3.2

Rubber particle size (µm) Rubber particle size (µm)


Asaprene 760AX

Rubber for super high-impact PSMolecular structure

Polybutadiene rubberBranched structureVinyl/cis/trans: 18/33/49Solution viscosity: 77cps


Asaprene 760AX

CharacteristicsBy using low-modulus Asaprene rubber, impact energy can be absorbed easily

6

7

8

9

10

11

12

10 15 20 25 30Modulus (kg/cm)

760AX

55AE

Constant rubber particle size

Izo

d im

pact

str

en

gth

(kg

•cm

/cm

)


Asaprene 670A (1)

Rubber for Super high-gloss HIPSTransparent HIPS

Molecular structureStyrene-butadiene rubber (39% styrene)Vinyl/cis/trans: 14/36/50Solution viscosity: 34 cps

CH2

HC C

H2C C

H2

HC

Ph

CH3

COR1

O COR2

O

Styrene unit Methacrylicester unit

Acrylic ester unit


Asaprene 670A (2)

CharacteristicsAllows for easy formation of core-shell rubber particlesMakes it easy to obtain transparent HIPSCorresponds to refractive Index of Styrene/Methacrylic copolymer and rubber phase

SP

Refractive Index

SBR PMMA PBA

1.59 1.54 1.49 1.46

Core-shell particles (thermal polymeri-zation)


Asaprene 625A (1)

Rubber for transparent HIPSMolecular structure

Styrene-butadiene rubber (35% styrene)Vinyl/cis/trans: 14/36/50Solution viscosity: 20 cps

CH2

HC C

H2C C

H2

HC

Ph

CH3

COR1

O COR2

O

Styrene unit Acrylic ester unitMethacryric ester unit

Rub.

Matrix Resin

Grafted Copolymer


Asaprene 625A (2)

CharacteristicsTransparency HIPS are easily obtained compared with other styrene-butadiene block copolymersEasier to handle:

• Bale is• Easier to cut• Less likely to crack• Bites into cutter

more easily

Refractive Index

SBR PMMA PBA

1.59 1.54 1.49 1.46

PS


Asaprene 720AX

Rubber for high-gloss mass ABSCharacteristics:

Easier to obtain small rubber particles

Molecular structure:Polybutadiene rubberVinyl/cis/trans: 18/33/49Solution Viscosity: 25 cps

Mass ABS with Asaprene720AX

720AX

730AX

R.P

.S.(µm

)

1

0.10 5 10 15 20 25 30 35 40

Relationship between Solution viscosity and R.P.S.Solution Viscosity (cps)


Asaprene 610A

Rubber for high-gloss mass ABSCharacteristics:

Easier to obtain small rubber particles

Molecular structureStyrene-butadiene rubber (15% styrene)Vinyl/cis/trans: 14/36/50Solution viscosity: 10 cps

Mass ABS with Asaprene 610A

R.P

.S.(µm

)

Relationship between Solution viscosity and R.P.S.

Solution Viscosity (cps)

610A

720AX730AX

1

0.10 5 10 15 20 25 30 35 40


H300A (1)

Rubber for HIPS with excellent thermal stabilityMolecular structure:

1,4-cis/trans: 63%1,2-vinyl: 1%Tetramethylene: 26%Butylene: 10%Solution viscosity: 75 cps

CH2

CH

CH

CH2

CH2

HC C

H2CH2

CH2

CH2

CH2

HC

HC

)( (( () ) )

CH2 H2C CH3

1,4-cis/trans 1,2-vinyl Tetramethylene Butylene


H300A (2)

0

2

4

6

8

10

12

14

PHBR

35AE

(73%)

(58%)

(89%)

(78%)

CharacteristicsHIPS and styreniccopolymer (e.g. mass-polymerized ABS) with PHBR have excellent thermal stability.As a result, the decline in impact strength is very small when molding at high temperaturesOutstanding capabilities for recycling applications

270°C X 30 290°C X 30 min min

Original Heat-aged Heat-agedIz

od

(kg

•cm

/cm

)


Asaprene 630A (1)

Rubber for translucent (high-gloss) HIPSMolecular structure

Styrene-butadiene rubber (22% styrene)Vinyl/cis/trans: 14/36/50Solution viscosity: 33cps

20

30

40

50

60

70

80

90

100

2 4 6 8 10 12 14 16

GoodCore-shell particle HIPS

Cell particle HIPS

Izod Impact (kg•cm/cm)

Glo

ss (

%)


Asaprene 630A (2)

CharacteristicsCore-shell rubber particles can be obtained easily

Comparison with other styrene-butadiene block copolymers:

Less rubber contentEasier to handle: Bale is

• Easier to cut• Less likely to crack• Bites into cutter more easily

Dissolving time is shorter

Core-shell particles


Asaprene 610A, 720AX (1)

Rubber used for mass ABSMolecular structure

610A• Styrene-butadiene rubber (15% styrene)• Vinyl/cis/trans: 14/36/50• Solution viscosity: 10cps

720AX• Polybutadiene rubber• Vinyl/cis/trans: 18/33/49• Solution viscosity: 25cps


Asaprene 610A, 720AX (2)

CharacteristicsSmall rubber particles the size of ABS are easily obtained, making it possible to obtain a high-gloss ABS

10

Polymerization Condition•Apparatus : 1.5L glass bottle•Composition : SM/AN/Rub.=65/25/10 (wt%)

••••••• •• Initiator:150ppm• •Chain Transfer:1200ppm

700A

730A

720AX

610A

R.P

.S.

(µm

)

1

0.10 10 20 30 40 50 60

Solution viscosity (CPS)

Relationship between Solution Viscosity and R.P.S.


Next Steps

Mitsubishi International offers a variety of outstanding synthetic rubbers for HIPS and Mass-ABS applicationsTo learn more about how MIC can meet your product needs, please contact us at (212) 605-2440, or email [email protected]

Thank you.

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Mitsubishi International Corporation - micchem.com · Mitsubishi International Corporation 2 Classification of Diene Rubber Polybutadiene (BR) High Cis BR Butadiene Rubber Styrene-Butadiene