Triazine Derivatives

Stephanie Schauhoff
EVONIK Degussa GmbH / Building Blocks
R&D and Applied Technology of Cyanuric Chloride & Derivatives

EVONIK Degussa GmbH

 Agenda
1. Introduction of peroxide crosslinking
2. Function of coagents
3. Introduction TAICROS® coagents
3.1. TAC
3.2. TAICROS
3.3. TAICROS M
4. Introduction TAICROS TMT
5. Flame Retardant TAICROS 6B
6. Degussa contacts

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 2

 1. Introduction of peroxide crosslinking
Crosslinking Mechanisms of Elastomers

Elastomers with double bonds Elastomers without double bonds

H2 C CH2
CH2 CH2
sulfur

Peroxide or energy
sulfur compounds
compounds

S CH
S CH
S S
S
S CH CH
S S S
S CH
S
S CH
S S S CH
CH
CH
CH
CH
CH CH
CH

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 3

 1. Introduction of peroxide crosslinking

Advantages
☺ Polymers with and without double bonds can be crosslinked

☺ Peroxide crosslinked rubbers have a higher heat and aging resistance

C-C 348 kJ mol-1
C-S 272 kJ mol-1
S-S 225 kJ mol-1

☺ Peroxide crosslinked rubbers provide a lower compression set

[used in all kinds of parts that have to withstand pressure (sealings) and
high temperatures (pipes, hoses in automotive applications)]

Disadvantages
 Higher vulcanization temperatures required

 Scorch time and vulcanization speed cannot be modified

 Sensitive against impurities and additives

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 4

 2. Function of coagents

 Coagent improves efficiency of peroxide crosslinking

 Coagent increases crosslinking density and speed of crosslinking

Rheometer curve of different crosslinking types

(silica filled EPDM formulation)

30

25

20
torque [dNm]

sulphur
peroxide + coagent
15

peroxide
10

0
0 5 10 15 20 25 30
time [min.]

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 5

 2. Function of coagents

 peroxide crosslinking improves aging resistance/heat resistance

 coagent increases this effect

Aging properties - change of modulus 200% after 7d@125°C Aging properties - decrease of Elongation at break after
7d@125°C

200

change of elongation at break [%]

80
change of modulus 200% [%]

180
160 70
140 60
120 50
100
40
80
30
60
40 20

20 10
0 0
sulphur peroxide peroxide + coagent peroxide + coagent sulphur peroxide peroxide + coagent peroxide + coagent

(4,5 phr TAICROS) (6 phr TAICROS) (4,5 phr TAICROS) (6 phr TAICROS)
crosslinking system crosslinking system

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 6

 2. Function of coagents

 peroxide crosslinking improves (=decreases) the compression set

 coagent increases this effect

Compression set 72 h/100°C

60

50
compression set [%]

40

30

20

10

0
sulphur peroxide peroxide + coagent peroxide + coagent

(4,5 phr TAICROS) (6 phr TAICROS)

crosslinking system

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 7

3. Introduction of TAICROS coagents

The TAICROS® family

Cyanuric chloride TAC TAICROS® TAICROS® 6B

O O O
Cl N Cl
N N N N Br N N Br
N N Br Br
O N O O N O O N O
Br
Cl

CH 3
Br
O

TAICROS® M N N
CH 3
O N O

CH 3
S

NH
TMT 15 TAICROS® TMT HN

S N S
H

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 8

 3. Introduction of TAICROS coagents
3.1. TAC (Triallyl Cyanurate)

FUNCTION
 coagent for peroxide crosslinking of elastomers e.g.
O EPDM, HNBR, EVA, chloroprene or TPE´s and for
N N
thermoplasts like PE or PVC
O N O  crosslinker for electron beam crosslinking of PE or TPE´s

ADVANTAGES
 lower compression set
 improved aging properties
 increased crosslinking density and yield
 crosslinking of saturated and unsaturated polymers

APPLICATION
 pipes and hoses, gaskets, damping materials
 cable coatings
 electronical components
 foams, shoe soles, floor heating pipes

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 9

 3. Introduction of TAICROS coagents
3.1. TAC (Triallyl Cyanurate)

Plastic application - Polyethylene

Dose - Gel curves for EB-crosslinking of PE

100
90
80
70
Gel content [%]

60
50
40
30
PE
20
PE + 2phr TAC
10
0
0 5 10 15 20 25 30
dose [kGy]

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 10

 3. Introduction of TAICROS coagents
3.1. TAC (Triallyl Cyanurate)

DELIVERY FORM
 TAC normal grade (solid m.p. 27 °C)
 TAC E 1200 (stab.)
 TAC liquid (melt at 35-40 °C)
 TAC DL 50/70 (powder, 50/70% on silica)

SPECIFICATION
 purity > 98 %

PACKAGING
 30 l plastic container
 200 l metal drum
 1 t IBC
 heated tank truck

HANDLING and STORAGE

 storage at <= 40°C
 remelting at 35-40°C

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 11

 3. Introduction of TAICROS coagents
3.2. TAICROS® (Triallyl Isocyanurate)

FUNCTION
O  coagent for peroxide crosslinking specially of elastomers

N N
with high processing temperatures e.g. fluoro rubbers

O N O
 crosslinker for electron beam crosslinking of polymers
with high process temp. (PA, PBT)

ADVANTAGES
 lower compression set
 improved aging properties
 increased crosslinking density and yield
 increased chemical and hydrolytic stability
 stable in the presence of acidic fillers

APPLICATION
 pipes & hoses (hydraulic, turbo air, fuel)
 suspensions (gear, motor)
 gaskets, sealings
 cable coatings (planes, cars, trains, high voltage)
 electr. components e.g. switch boards

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 12

 3. Introduction of TAICROS coagents
3.2. TAICROS® (Triallyl Isocyanurate)

Rheometer curve of different coagents

30

25
TAC
20
torque [dNm]

TAICROS
15

10
peroxide
5

0
0 5 10 15 20 25 30
time [min.]

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 13

 3. Introduction of TAICROS coagents
3.2. TAICROS® (Triallyl Isocyanurate)

ADVANTAGES of TAICROS® over TAC

Therm al stability of Triazine
crosslinkers at 200°C
 higher thermal stability / higher processing
100
temperatures
monomer content [%]

80
 improved stability against basic or acidic
60
fillers
40 TAC
TAICROS
 improved hydrolytic stability
20

0
 more hydrophobic
0 1 2 3 4 5 6 7 8 9
 specially suitable for fluoro rubber
tim e [h]
 can be used for electron beam cross linking
of PA and PBT

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 14

 3. Introduction of TAICROS coagents
3.2. TAICROS® (Triallyl Isocyanurate)

Plastic application - Polyamide

Crosslinking degree of PA 12 by EB with TAICROS

100

80
Gel Fraction [%]

60

40
4% TAICROS
20
2% TAICROS
0
0 50 100 150 200 250
Dose [kGy]

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 15

 3. Introduction of TAICROS coagents
3.2. TAICROS® (Triallyl Isocyanurate)

PRODUCT QUALITIES
 TAICROS® (liquid m.p. 25 °C)
 TAICROS® E 1000 (stab.)
 TAICROS® DL 70 (70% on silica)

SPECIFICATION
 purity > 99 %

PACKAGING
 30 l plastic can
 200 l metal drum
 1 t IBC (heatable if required)

HANDLING and STORAGE

 storage at <= 40°C
 remelting at 35-40°C

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 16

 3. Introduction of TAICROS coagents
3.3. TAICROS® M (Trimethallyl Isocyanurate)

APPLICATION
C H3
O
 coagent for peroxide or EB crosslinking of
N N polymers with high processing temperatures
C H3  crosslinker for fluoro rubbers e.g. biodiesel
O N O
resistant FKM´s
 crosslinker for polyamide for high temperature
C H3 applications

ADVANTAGES
 easy handling: fine powder
 high thermal stability
(low tendency for homopolymerization)
 improved compression set
 excellent aging properties

REGISTRATION STATUS
 TSCA listed
 EU full registration in progress

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 17

 3. Introduction of TAICROS coagents
3.3. TAICROS® M (Trimethallyl Isocyanurate)
Specification

 purity >= 95 %

Typical Properties

 white crystalline powder

 m.p. 74 – 82,5 °C
 b.p. @1013 hPa > 310 °C
 vapor pressure @175°C 7 hPa
 water solubility 0,07 g/l

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 18

 3. Introduction of TAICROS coagents
3.3. TAICROS® M (Trimethallyl Isocyanurate)

N
O

N
TAC
DE = 4,80
O N O
incr

incr
eas

N N
TAICROS®

eas
ing

O N O
DE = 2,36

ing
hyd

the
CH3
rop

rma
N N
hob

CH3
N TAICROS® M

l sta
O O
ic
pro

bil
CH 3

ity
per
ty

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 19

 3. Introduction of TAICROS coagents
3.3. TAICROS® M (Trimethallyl Isocyanurate)

Thermal Stability

Thermal stability of Triazine crosslinkers at 250°C

100
TAICROS
80 TAICROS-M
content [%]

60

40

20

0
0 5 10 15 20 25
storage time [min.]

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 20

 3. Introduction of TAICROS coagents
3.3. TAICROS® M (Trimethallyl Isocyanurate)

Formulation Guideline for Fluoro Rubber

Fluoro rubber 100

Thermal Black N 990 20 - 30

TAICROS M 2-5

Peroxide
1,0 - 2,5
2,5-dimethyl-2,5-di-(t-butylperoxy)hexane

Cure Conditions

Press cure 10 min. 160°C - 15 min. 180°C

Post cure 2 - 4 h 180°C

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 21

 3. Introduction of TAICROS coagents
3.3. TAICROS® M (Trimethallyl Isocyanurate)

Plastic application - Polyamide

Formulation Guideline

Poyamide 12/6/66/46 100

TAICROS M 2-5

Electron Beam curing

Dose 60 - 120 kGy

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 22

 4. Introduction of TAICROS TMT

Crosslinker for Chlorine Containing Elastomers

S
APPLICATION
HN NH  crosslinking agent for ECO, chloroprene
 substitute for lead/ ETU
S N S
H  support elimination of lead in cars
 application in combination with MgO/CaCO3

PROPERTIES
 fine yellow powder
 m.p >280°C (decomposition)
 ignition temperature: 380°C
 solubility in water: 0,83 g/l

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 23

 4. Introduction of TAICROS TMT

Standard Specification (based on oil-free material)

 Appearence (visual) yellow powder
 Content (titration) >= 98,0 %
 Ash content <= 0,1 %
 Volatiles (IR dryer) <= 0,3 %

Typical Data

 Oil coating ca. 2 %

 DOP 35 – 55
 Particles size < 63µm >= 99 %

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 24

 4. Introduction of TAICROS TMT

Postulated crosslinking mechanism

CH2-CH-O
CH2
S
S

Acid acceptor N N
CH2-CH-O + HN NH CH2 CH2
-HCl
CH2Cl S N S CH CH2 S N S CH2 CH
H
O O

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 25

 4. Introduction of TAICROS TMT

TOX data and safety

property TAICROS TMT ETU

S
S

HN NH
HN NH
S N S
H

labeling none Toxic (T)

LD50 rat oral 9.500 mg/kg 710 mg/kg
skin irritation not irritating slight irritation
eye irritation not irritating slight irritation
gene toxicity in vitro not testet mutagen
carcinogenicity not testet carcinogen
teratogenicity not testet teratogen

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 26

 4. Introduction of TAICROS TMT

Formulation

ECH/EO 100

carbon black 50-100

plasticizer DBEEA (Di(butoxy-ethoxy-ethyl)adipate) 0 - 20

NBC (Ni-butydithiocarbamate)
stabilizer MMBI (methylmercapto-benzimidazol) 0-2
TMQ (Trimethyl-dihydrochinolin)

processing aid stearic acid 1

crosslinker TAICROS TMT 0,8

CaCO3 5
acid acceptor
MgO 3

activator/accelerator DPG (diphenylguanidine) 0-1

retarder CTP (N-(cyclohexylthio)phthalimid) 0 - 0,5

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 27

 5. Flame Retardant TAICROS 6B

Br N N Br FUNCTION
Br
O N O
Br  flameretardant for polyolefins (PP, PE, PS)
Br
ADVANTAGES
Br
 high thermal stability
 no decomposition during processing
 not persistant in nature
 no dioxine formation
 excellent flame retardancy and aging properties

APPLICATION
 all kind of flame retarded PP-parts e.g. computer
housing

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 28

 5. Flame Retardant TAICROS 6B

SPECIFICATION
 appearence (Visual) white powder
 Bromine content (Titration) >= 64,7 %
 Color (Apha) <= 50
 Bromide content (Titration) <= 300 ppm
 Volatiles (IR drier) <= 0,2 %

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 29

 5. Flame Retardant TAICROS 6B

FORMULATION in PP to meet UL-94 V2

 2% TAICROS 6B
 1% Sb2O3

FORMULATION in PP to meet UL-94 V0

 6% TAICROS 6B
 3% Sb2O3

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 30

 Degussa contacts:

Product Manager Cyanuric Chloride & Derivatives

Dr. Manfred Schmidt
Phone + 49 - 69 - 218 - 3277
Email: manfred.schmidt@evonik.com

R&D Cyanuric Chloride & Derivatives

Dr. Stephanie Schauhoff
Phone + 49 - 6181 - 59 - 4005
Email: stephanie.schauhoff@evonik.com

Presentation Triazine Derivatives only products.ppt 23.05.2007 EVONIK Degussa GmbH 31