Styrenic Copolymers having Maleic Anhydride

Units as Reactive Compatibilizer for ABS and

Engineering Plastic Alloys

Kohhei Nishino, DENKI KAGAKU KOGYO K.K.

The 3rd International Summit of Polymer Compatibilization Technology

Shanghai China, Sep 1, 2015
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Denka’s Company Profile

Name DENKI KAGAKU KOGYO K.K.

Established May 1, 1915

Net Sales（Fiscal Year 2014） USD 3,494 Million*

Net Income（Fiscal Year 2014） USD 172 Million*

Employees 5,309
* Exchange rate : 109.9 Yen/USD

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Denka’s Business
Elastomers & Elastomers
Performance Plastics Acetylene Black
Styrenic Polymers
Styrene & Acetyl Chemicals

Infrastructure & Cement

Special Cement Additives
Inorganic Materials
Inorganic Chemicals
Agri-Products

Electronics & Functional Films

Advanced Specialty Materials
Innovative Products
Electronic Products
Adhesives & Solutions

Life Science & Housing Materials

Environment Products Industrial Materials
Household Packaging
Medical Science
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Denka Styrenic polymers
DENKA STYROL（GPPS） DENKA TX Polymer（MS）

Ultra high impact strength（MW-1）
Excellent transparency

Easy Processing
Good weather resistance
Light Guide Plate for LCD-TVs

DENKA MABS (Transparent ABS) DENKA MBS

Excellent clarity and toughness
High impact and Easy Processing

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Denka Styrenic polymers
CLEAREN（SBC） DENKA IP

Good Flexibility
Heat resistant modifier for ABS, ASA

Miscible with standard PS
Compatibilizer for PA6/ABS

* SBC is Styrene Butadiene block copolymer.

DENKA is the global styrenic supplier. We offer the portfolio

of styrenic specialties. We can provide various styrenic with
transparence, high heat resistance and so on.

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Denka IP
Denka IP is the copolymer developed by Denka’s unique technology.

NPMI Sty MAH

Denka IP

Major characteristics
Miscible with SAN, ABS, ASA …
High heat resistance （ Tg : 196℃） and good thermal stability

Main application
Heat resistant modifier for ABS, ASA ⇒ High heat ABS
Compatibilizer for ABS and Engineering Plasitic alloys（e.g. PA6/ABS）
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Denka “RESISFY”
RESISFY is a specialty styrenic copolymer developed by Denka’s technology.
＜Characteristics＞
‣ Miscible with PMMA, ABS
‣ High Heat Resistance
‣ High Transparency

＜Application＞
‣ Heat Resistant Modifier of PMMA
‣ Touch Panel Cover Sheet（PMMA/PC）

‣ Polarizer Protective Film

‣ Optical Lenses Polarizer Protect Film

‣ Automotive Meter Panel

‣ Piano-Black Resin
‣ Compatibilizer 7
Outline

Background

Denka IP as Reactive Compatibilizer

Experimental

Properties of PA6 / ABS Alloy modified with Denka IP

Summary

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Background

ABS resin has been widely used for engineering plastic alloys
such as PC/ABS, PA/ABS, and PBT/ABS for improving deficient
characteristics of a particular material.

Crystalline plastics such as PA and PBT are immiscible with

ABS. However, compatible alloys can be achieved with reactive
compatibilizers which have functional groups such as cyclic
anhydride and epoxide.

To obtain industrially useful alloys, the selection of optimal

reactive compatibilizer and reaction control are important.

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Denka IP as Reactive Compatibilizer

Reactive Compatibilizer for immiscible polymer blend

Miscible pair Reaction Graft Copolymer

PA C
N
ABS “Denka IP” -NH2
C
C

O=
C
C- O
-OH
PMMA,MBS “RESISFY”
C - OH
PC PBT

O=
‣ Graft copolymer can be formed in situ during extrusion process.
‣ As the results, compatibility of immiscible polymer blend can be improved.

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Formation of IP-graft-PA6 copolymer

IP PA6 IP-graft-PA6
Extrusion

（（（（
（（（（

C C
C C
O + （CH2）5 CNH
H2N（ （CH2）5 CNH
N（ + H2O
C C
C O C O

））））
））））

Other Maleimide type/PA6=35/65 Denka IP/PA6=35/65

（without MAH） （with MAH）

1.7µm 1.7µm

Denka IP is well dispersed into PA6 matrix because of reaction between IP and PA6.
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Experimental
Materials

Denka IP : Standard, High Flow
ABS : Graft-ABS （PBd > 50%）

PA6 : Standard, High Flow
SAN : Standard

Compounding

Extruder : 35mm Twin Screw
Screw Speed : 250 rpm

Cylinder Temperature : 270℃
Discharge Rate : 25kg /h

PA6 Graft ABS, SAN

IP

mixing

M Twin Screw Extruder PA6 / ABS Alloy

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Injection Molding

Cylinder Temperature : 250℃ or 260℃

Mold Temperature : 60℃

Evaluations

Mechanical and Thermal Properties : ISO method

Conditioning : 16h at 23℃ / 50% relative humidity

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Properties of PA6 / ABS Alloy

Impact Properties Ductile Fracture

Ratio PA/Graft ABS Unit 50/50 60/40 70/30

Content of IP % 0 3 0 3 0 3
Tensile Strength MPa 22 29 28 35 35 40
Flexural Modulus MPa 900 1,110 1,060 1,180 1,360 1,530
HDT 0.45MPa (without annealing) ℃ 77 83 80 87 86 107
* PA6 : Standard Grade 14

Effect of Denka IP concentration

* Denka IP : High Flow , ABS : Graft ABS , PA6/ABS=50/50

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Examples of PA6/ABS Alloy modified with IP

Standard High Stiffness

unit Example-1 Others-1 Example-2 Others-2
IP High Flow wt% 5 5
PA6 High Flow wt% 48 48
ABS Graft-ABS (PBd >50%) wt% 35 30
SAN Standard wt% 12 17
MFR 240℃, 98N g/10min 54 32 67 36
Tensile Stress at Yield MPa 38 37 41 43
Elongation at Break % >200 >200 112 74
Flexural Modulus MPa 1,520 1,530 1,660 1,680
Notched Charpy Impact Strength kJ/m2 73 32 64 28
Vicat Softening Temp, 50N ℃ 113 103 116 106
※Values are typical and not guaranteed.

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Denka IP allows well-balanced properties of PA6/ABS

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Summary

Denka IP has been widely used as reactive

compatibilizer for PA6/ABS alloy.

IP-graft-PA6 copolymer can be formed in situ during

the extrusion processing of PA6/ABS alloy because of
maleic anhydride groups of IP.

As the results, ABS domains in alloy become smaller

and super-tough PA6/ABS alloy can be obtained.

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Thank you for your attention !

e-mail : [email protected]
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