COMPOUNDING OF ECO

Vulcanization Method

a. Vulcanization By Amine Derivates

I I I
CH2 CH2 CH2
I I I
2CHCH2 – Cl + NH2 RNH → CHCH2 – NHRNHCH2 – CH –
I I I
O O O
I I I

Ex : DIAK No. 1 / DLP

b. Vulcanization by Cyclic Thiourea

NH

CHCH2 O – + C – SH → - CH2 – CHO - N

I I
CH2 N CH2 – S – C
I
Cl HN

- CH2 – CHO –
I
CH2 – S – CH2
I
- C H2 – CH – O

Ex: ACC #22 / Pb3O4 / ( ACC CBS )

c. Vulcanization by Polythiol

I I I
CH2 CH2 CH2
I I I
2CH – CH2 – Cl + HS – R – SH → CH – CH2 – S – R – S – CH2 – CH
I I I
O O O
I I I

Ex : Zisnet F / HgO / CaCO3 / PVI

ECHO – S , ECHO – P /BaCO3
Daisonet XL-21 / Pentaeritritol / Ca(OH)2 / PVI
 Crosslinking Agent For Epichlorohydrin Rubber
Ethylene Thiourea 2,4,6 – Trimercapto 6-Methylquinoxaline- 2,3 -
( ETU ) -S-triazine ( Zisnet F ) dithiocarbamate
(Daisonet XL-21 )

H SH
N
N S
S N N
Chemical structure O
N N S
H HS N SH

Toxicity ( LD50 ) 250 mg/kg ( rat ) 570 mg / kg ( rat ) 2500 mg / kg ( rat )

Cure System

6-Methylquinoxaline-2,3-
Ethylene thiourea 2,4,6-Trimercapto-s-
dithiocarbamate
( ETU ) triazine ( Zisnet F )
(Daisonet XL-21)

DHT-4A
Acisd aceptyor Pb3O4 MgO
(synthetic hydrotalcite)

P-152
Accelerator TMTM
(DBU-salt of phenolic resin)
Nocticer SS
Retarder PVI PVI
or CBS

- Compression set
Good balance of Long term heat
Advantage - Long term heat resistance
physical properties resistance
- Low toxixity

- Toxicity
Disadvantage Self life Cost performance
- Mold Fouling
 Cure System For Bond to FKM
Bis-Phenol
2,4,6-Trimercapto-s- (Dynamar FX 5166,
Thadiazole
triazine ( Zisnet F ) Dynamar FC 5157)

Less scorch time

w/o Barium
Dis advantage Slightly lower tensile Expensive
carbonate
(heavy metal)

Non toxic
Advantage Non toxic Easily adjusted cure Non toxic (Dynamar RC5251Q)
rate

Adhesion to
Fair - Good Excellent
FKM

Addition 3 phr of Zeonet PB will be effective to enhance adhesion to FKM

Lab Adhesion of CO/ECO/GECO to FKM

Adhesion strength by cure system

Polymer 2,4,6-Trimercapto-s-
Lead / ETU Thiadiazole Bis-Phenol
Type triazine ( Zisnet F )

CO No Bond No Bond No Bond 3.5

ECO No Bond No Bond 1.4

GECO 0.4 No Bond No Bond 5.4

Bond is kN/m, Cure systems are non-lead except where indicate

Factory adhesion values may be higher
 Adhesion ECO & GECO to FKM
Ingridients 1 2
GECO 100
ECO 100
N 762 65 65
1,2-dihydro-2,2,4-trimethylquinoline (TMQ) 1
Nickel dibutyldithiocarbamate (NBC) 1
2-mercapto-4(5) methylbenzymidazole (MMB) 1 1
Stearic acid 2 2
Calcium hydroxide 3 3
Calcium oxide 85% active 2.5 3.0
Potassium stearate (NONSERL SK-1) 3 3
TMPTMA (Methacrylate coagent) 0.5 0.5
2(Di-tert-butylperoxyisopropyl) benzene -40% 1.2
Calcium carbonate / DPG 5 / 0.5
2,4,6-trimercapto-s-triazine (85% active) 1
Peel strength, kN/m

Daisonet XL-21
Properties of Daisnonet XL-21 :
Melting point : 169.8 – 170 °C
Toxicity LD50 (rat) : 2500 mg/kg

Recommended Ingredients:
Advantages :
Daisonet 21S : 1.7 phr
Low toxicity
P-152 : 1.0 phr
No mold fouling
PVI : 1.0 phr
Excellent compression set
DHT-4A : 3.0 phr
Improved heat resistance
MgO : 3.0 phr
(only in case of
vulcanization
by hot air or steam )
 Antioxidant

Nickel compound (Nocrac ) NBC Nickel dibutyl dithiocarbamate

(Nocrac ) 224 Polymerized trimethyl dihydroquinoline
Quinoline derivates
(Nocrac) AW 6-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline

(Nocrac) 810NA N-Isopropyl-N’-phenyl-p-phenylenediamine

Sec-Aromatic amines
(Nocrac) DP N,N’-Diphenyl-p-phenylenediamine

(Antage #2) 2,2’-Methylene-bis-(4-methyl-6-tert-

W-400 butylphenol)
Phenol derivates (Antage ) 4,4’-Phiobis-(6-tert-butyl-3-methylphenol)
Crystal

Mercanpans (Nocrac) MB 2-Mercaptobenzimidazole

Test Condition : static, 50% Elongation, 40°C, 80 pphm

Evaluation : JIS K 6301

NC : Not crack
A : a small number of crack
B : a large number of crack
C : numberless crack

1 : observed with 10 magnifications

2 : observed with the naked eye
3 : length of crack is less than 1 mm
4 : length of crack is less than 3 mm and over 1 mm
5 : length of crack is over 3 mm

e : neighborhood of edge
ex : eB-2
 Ozone Resistance
Control NBC 224 AW 810NA DP W-400 Crystal MB
(24h)
Epi. H NC NC NC NC NC NC NC NC NC
Epi. C NC NC A-1 C-1 B-2 NC NC NC NC
C-2 C-2 A-1 A-1 A-1 C-1
Epi. CG NC NC NC NC NC A-1 NC NC NC
C-2 A-1 B-1 A-1 A-1

(96h)
Epi. H A-1 NC A-1 A-1 NC NC NC NC NC
A-1 A-1 A-1 A-1
Epi. C NC NC A-2 C-2 C-3 B-1 NC NC NC
C-1 A-3 B-2 C-1 C-1 C-1
Epi. CG NC NC NC C-2 NC B-2 NC A-1 A-1
A-1 A-1 A-1

Ozone Resistance
Control NBC 224 AW 810NA DP W-400 Crystal MB
(288h)
Epi. H B-1 NC NC A-2 NC A-1 A-1 A-1 A-1
A-1 B-2 A-1 eB-2
Epi. C C-1 NC A-3 C-2 C-4 B-2 C-1 C-1 C-1
A-1 B-3 C-2
Epi. CG NC NC NC C-2 A-1 B-2 A-1 A-1 C-1
A-1 eA-2 B-3
(384h)
Epi. H B-1 NC NC A-2 NC A-1 A-1 A-1 A-1
A-1 B-2 A-1 eB-2 B-1
Epi. C C-1 NC A-4 C-2 C-4 C-2 C-1 C-1 C-1
C-2 A-1 B-4 C-3 C-3 C-2
Epi. CG A-1 NC NC C-2 A-1 B-3 A-1 A-1 C-1
eA-3
 Comparison of Plasticizer
801 802 803 804 805 806 807
Epichlomer C 50 ← ← ← ← ← ←
Epichlomer H 50 ← ← ← ← ← ←
N 550 55 ← ← ← ← ← ←
ADK cizer RS-107 4 ← ← ← ← ← ←
Polycizer W-305 ELS 8 ← ← ← ← ← ←
Polycizer PE-330 8
Merrol P-6420 8
Plasthall P-643 8
Paraplex G-54 8
Paraplex G-56 8
Paraplex G-57 8
Plastrodine S 1 ← ← ← ← ← ←
Sorbitan monostearate 2 ← ← ← ← ← ←
NBC 1 ← ← ← ← ← ←
Pb2O4 5 ← ← ← ← ← ←
ETU 1.4 ← ← ← ← ← ←
Added into
Noctizer SS 2 roll mill 0.5 ← ← ← ← ← ←

801 802 803 804 805 806 807

Mooney scorch test ML @ 125 °C
V min 48 51 54 54 54 55 55
T5 (minutes) 11.8 11.0 10.6 10.0 10.5 10.5 10.5

Cure condition :
1st cure : 15 min/170°C (CS 20 min)
2nd cure: 2 hr / 150°C
 801 802 803 804 805 806 807
Original properties
< 1st Cure >
TB (MPa) 13.1 13.3 13.1 13.4 13.6 13.5 13.2
EB (%) 545 595 580 550 620 595 550
HS (shore A) 71 72 72 72 72 72 71

< 2nd Cure >

TB (MPa) 15.9 15.4 15.4 15.4 15.2 15.6 15.4
EB (%) 400 395 370 365 365 390 370
HS (shore A) 73 74 74 74 73 75 75

Compresison set 22h, 100°C

< 1st cure > 37 38 38 39 38 39 39
< 2nd cure > 12 12 12 13 13 12 12

801 802 803 804 805 806 807

Aging 100h, 110°C < 2nd cure>
∆W (%) - 0.7 - 0.7 - 0.7 - 0.6 - 0.7 - 0.6 - 0.7
∆TB (%) +7 +6 +9 +8 + 11 +8 +9
∆EB (%) -6 - 15 -5 -7 -3 -9 -8
∆HS (point) +3 +1 +2 +1 +3 +1 +1

Aging 100h, 150°C

W (%)
∆W - 2.5 - 2.5 - 2.5 - 2.5 - 2.5 - 2.5 - 2.5
∆TB (%) -25 - 18 - 19 - 20 - 17 - 22 -20
∆EB (%) -41 - 38 - 34 - 36 - 33 - 41 -34
∆HS (point) +5 +3 +4 +4 +6 +3 +4

Diesel Fuel 48h, 23°C < 2nd cure> dry out 24h at 80°C
∆W (%) - 0.6 - 0.5 - 0.6 - 0.4 - 0.5 - 0.4 - 0.5
∆TB (%) -3 0 -3 +1 0 -1 -1
∆EB (%) -9 -5 -3 -1 -3 -7 -5
∆HS (point) +2 0 0 +1 +2 0 0
 801 802 803 804 805 806 807
Low temp. properties < 2nd cure>
@ impact brittleness (in MeOH bath)
Brittleness Temp. (°C) -39 - 35 - 34 - 31 - 42 - 36 -33
All specimens broken (°C) - 42 - 36 - 36 - 34 - 44 - 38 -36
No specimen broken (°C) - 36 - 32 - 30 - 28 - 40 - 34 - 30

Low temp. bending ( hold on 24h, at – 35 °C )

- No Crack -

Gehmann torsion test ( in MeOH bath )

T2 (°C) -29 -30 -29 -30 -29 -30 -28
T5 (°C) -36 -36 -36 -37 -36 -35 -36
T10 (°C) -39 -39 -38 -39 -38 -38 -38
T100 (°C) - 43 - 43 - 43 - 43 - 45 - 45 - 45

Affinity of Elastomers (bond strength)

SBR NBR CPE ECO ACM FKM

SBR - - 0.6 Poor - -

NBR - - 4–5 - - -

CPE 0.6 4–5 - 5 2.5 Poor

ECO Poor - 5 - 9 -

ACM - - 2.5 9 - -

FKM Poor - Poor - - -

T – Peeling
Bond strength : kg / inch
Peeling speed : 50 cm / min
Cure condition : 160 °C x 30 minutes ( steam cure )
 Appendix
Trade Name Function Chemical Name Maker
PZ Vul. Agent or ACC Zn dimethyldithio carbamate Ohuchi Shinkoh Kagaku Co.

TTPE Vul. Agent or ACC Ferric dimethyldithio carbamate -ditto-

VULNOC AB Vul. Agent Ammonium benzoate -ditto-

DIAK No.1 Vul. Agent Hexamethylenediamine carbamate Du Pont USA.

DIAK No.3 Vul. Agent N,N-dicinnamilidene-1,6-hexane diamine Du Pont USA.

TRIMENE BASE Vul. Agent Reaction product of ethylchloride, Uniroyal USA

formaldehyde and amonia

NA 22 Vul. Agent 2-mercapto imidazoline Uniroyal USA

MINIUM Acid aceptor Lead oxide

TRA Vul. Agent or ACC Dipentamethylene thiuram hexasulfide

SULFAX PMC Vul. Agent or ACC Surface treated sulfur Tsurumi Kagaku Kogyo Co.

NONSERL SK-1 Vul. Agent Potassium stearate Nippon Oil & Fat Co

NONSERL SN-1 Vul. agent Sodium stearate -ditto-

Appendix
Trade Name Function Chemical Name Maker
NS SOAP Vul. Agent Sodium stearate Toa Paint Co.

RF-3752 Vul. Agent Trimercaptocyanurate

BZ ACC Butyl Zimate

PVI Retarder N-Cyclohexylthiophalimide

VULKALENT E/C Retarder Sulphoneamide derivates Lanxess

NAUGARD Antioxidant Diphenylamine derivates Uniroyal USA.

#445
NOCRAC #630S Antioxidant Mixed phenylenediamine Ohuchi Shinkoh Kagaku Co.

SILANE A-189 ACC γ-Mercaptopropyltrimetoxylane Union Cabide USA

SILANE A-1100 ACC γ-Aminopropyltrimetoxilane -ditto-

WB-16 Lubricant Metal salt of higher fatty acid Struktol

WB-212 Lubricant Higher fatty acid ester Struktol

TE-58A Lubricant Oil paste of metal salt of higher fatty acid Technical USA

TE-80 Lubricant -ditto- -ditt0-

 Appendix
Trade Name Function Chemical Name Maker
SUN-ADE LP, Lubricant Higher fatty acid ester Sanshin Kagaku Kogyo Co.
HP
EXTON K-1 Lubricant Metal salt of higher fatty acid Kawaguchi Kagaku kogyo

HI-MIC #1070, Lubricant Micro crystaline wax Nihon Seiroh

#1080

ARMOWAX EBS Lubricant Ethylene-bis-stearomide Lion Aczo

BANLUB N-18 Lubricant -ditto- Hariwa Kasei

THIOKOL TP- Plasticizer Polyester Thiokol USA

735
ADEKACIZER Plasticizer Polyester Adeka-Argus Jpn.
RS-735

CELITE 505 Filler Diatomaceous earth John Manville USA

CRYSTALITE Filler Silica Tatsumori Co.

VXS-2

MISTRON Filler Talc Cyprus industrial mineral

VAPOR USA.

CYPRUBOND Filler Surface treated talc with silane -ditto-

Appendix
Trade Name Function Chemical Name Maker
Zeonet PB Tackifier to FKM Tetra n-butyl phosponium Nippon Chemical Industry
benzotriazolate Ethylene glycol 1.5 wt%
Dynamar FX Curative Phosponium salt 3M USA
5166
Dynamar FC Curative Bis phenol 3M USA
5167
Dynamar RC Acid Non lead acid 3M USA
5251Q aceptor/activator