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Triallyl Isocyanurate
TAIC®
TAIC® is the trade name of the product TRIALLYL ISOCYANURATE.
TAIC® is a symmetric polyfunctions triazine compound which has been
used for the crosslinking reaction of synthetic rubbers and plastics
as well as a raw material for flame retardant. TAIC® possesses a
thermally stable triazine ring and unique properties, providing
a polymer with improved properties, including heat resistance, mechanical
properties and resistance to hydrolysis and weathering.
| Properties
of TAIC® |
| C.A.S.
No. |
1025-15-6 |
| TSCA No. |
1025-15-6 |
| EINECS
No. |
2138347
|
| Appearance |
Slightly
yellowish and transparent liquid above 30°C |
| Specific
Gravity |
(D) See
Fig. 1 |
| Boiling
Point |
144°C
at 3 mmHg (see Fig. 2) |
| Flash Point
|
245°C
by Pensky-Martens method |
| Viscosity |
See Fig.
3 |
| Specific
Heat |
0.6 cal/g
°C at 40°C |
| Refractive
Index |
(nD30)
1.5070-1.5100 |
| Solubility
|
| Water |
0.34% at 30°C |
| n-Pentane |
Slightly soluble |
| Ethylene Glycol |
Slightly soluble |
| Benzene |
Soluble |
| Xzylene |
Soluble |
| Methanol |
Soluble |
| Methly Ethyl Ketone |
Soluble |
| Heptane |
Soluble |
|
| Fig. 1 Specific Gravity of TAIC® |
Fig. 2 Vapor Pressure of TAIC® |
 |
 |
| Fig. 3 Viscosity of TAIC® |
|
|
| Fig. 4 Infrared Spectrum
of TAIC® |
 |
|
A. Polymerization
Reaction
TAIC® is a poly-functional allylic monomer and is easily polymerized
by using radical polymerization catalyst such as organic peroxide
and azocompound.
TAIC® is less reactive than other vinyl-type monomers. Q and e values
of TAIC® are 0.011 and -0.60 respectively. (1)
The heat of polymerization is 55.5 Kcal/mol.
1) Bulk Polymerization
In the reaction of bulk polymerization by using peroxide catalyst,
TAIC® provides such a transparent and hard but brittle homopolymer,
which has very excellent heat resistance such as that only 5% of weight
loss at 400oC in nitrogen atmosphere by thermal gravimetric analysis.
(Fig. 5)
| Fig. 5 Thermal Analysis
of TAIC® Homopolymer |
 |
| Operation
Condidtions |
Sample
Weight |
15mg |
TGA: Thermal
Gravimetric Analysis |
| |
Sample
Cell |
Pt |
DTA: Differential
Thermal Analysis |
| |
Reference
Material |
Al2O3 |
|
| |
Heating
Rate |
10°C/min. |
|
|
2) Solution Polymerization
The polymerization of TAIC® in common solvents provides homopolymers
having particularly high melting points. (2)
When the polymerization of TAIC® is carried out in solvent such as
halogenated hydrocarbons or aldehydes, linear polymers may be produced
by the telomerization with free radical of the solvent. By taking
advantage of this telomerizarion, prepolymers which have molecular
weith of 6,000 to 9,000, melting point of 120 to 150°C and bromine
value off 25 to 35 can be produced. (3)
3) Copolymerization
TAIC® can be copolymerized with many vinyl and allyl type monomers
to give copolymers having different properties. (Fig. 6) (4) The copolymerization
of TAIC® with other vinyl type monomer is camparatively difficult to
be proceeded, however, TAIC® can be used practically for over various
fields of application in which small amount of TAIC® participation
is enough for the purposes. The copolymers thus produced has higher
melting point and specific properties.
| Fig. 6 Copolymer Composition Curves
of TAIC® |
|
|
B. Crosslinking Reaction
TAIC® is broadly utilized as a crosslinking coagent for peroxide or
radiation crosslinking of polyolefines and synethetic rubbers.
Main role of a crosslinking coagent is inprovement of the crosslinking
efficiency by behaving longer life radicals vai primary radicals.
The effectiveness of allylic crosslinking coagent is much more superior
to vinyl compound by following reasons:
a) Radicals created in allylic compounds are stabilized by the allyl
resonace, density of
radical in the system is kept in high level.
b) In case of vinyl monomer, the polymerization takes place easily
among mutual monomers
and so the effectivness to crosslinking reaction
will turn worse.
TAIC® can be combined with rubber molecule by crosslinking reaction
and improve physical properties include heat resistance, weathering
resistance and resistance to oil.
TAIC® is employed as a crosslinking coagent for halogen containing
rubbers such as chlorinated polyethylene (CPE) and fluoroelasteomer,
some parts of allyl double bonds left in the crosslinking system act
as the acceptor of acidic substances such as HCI and HF liberated
from the rubber, and physical properties of crosslinked rubber is
much improved.
C. Addition Reaction
Addition reaction to double bonds of TAIC® takes place in the same
way as to common olefine compounds.
Halogenated TAIC® such as Tris (2,3-dichloro propyl) isocyanurate and
Tris (2,3-dibromopropyl) isocyanurate are important compounds as flame
retardants for plastics. (Table 1)(5)
| Table 1 Properties of
Halogenated TAIC® |
| X |
Br |
CL |
| Molecular
Weight |
729 |
462 |
| Melting
Point (°C) |
110-120 |
94-96 |
| Content
of Halogen (WT%) |
66 |
46
|
 |
| Cyclopentadiene
can be added to TAIC® by Diels Alder's reaction. |
|
| Product
Specifications |
| TAIC®
|
| Appearance |
Slightly yellowish and transparent
liquid state in summer and white solid in other seasons |
| Color (APHA) |
Max. 70 |
| Specific Gravity
(30°C) |
1.15 - 1.17 |
| Viscosity (30°C, cp) |
80 - 110 |
| Melting Point (°C) |
23 - 27 |
| Moisture (%) |
Max. 0.1 |
| *Di-t-butyl hydroxy toluene
(BHT) is added as much as 100 ppm to TAIC® as a stabilizer |
|
A. Crosslinking Coagent
TAIC® is widely used as a coagent for peroxide crosslinking or radiation
crosslinking of Chlorinated Polyethylene (CPE), EPDM, Fluroelaster
and so on.
1) Polyolefines
TAIC® is availavle for linking by x-ray, y-ray electron or ultra violet
ray radiation and the product polyolefines have the superior insolubility
to solvents and the tensile strength at high temperature could be
improved. (6)
2) Chlorinated Polyethylene (CPE)
TAIC® is effective modifier to heat resistance with increasing of crosslinking
density for peroxide crosslinking denisty for peroxide crosslinking
of CPE. Since TAIC® acts as an acceptor of HCI which is envolved from
CPE at crosslinking reaction and deterioriates its physical properties.
Table 2 is an example of crosslinking of CPE using TAIC® (7).
3) Ethylene Vinyl Acetate Copolymer (EVA)
TAIC® is the most effecdtive coagent for crosslinking EVA. The effectivness
of crosslinking coagent which acts in peroxide crosslinking of EVA
is as follows; (10)
TAIC® = TAC > DVB => TMPTMA = DAP = EGDM > NON
TAIC®: Triallyl isocyanurate
TAC: Triallyl cyanurate
DVB: Divinyl Benzen
TMPTMA: Trimethylolpropane trimethacrylate
DAP: Diallyl phthalate
EGDM: Ethyleneglycol dimethacrylate
NON: None of crosslinking coagent
And Fig. 7 shows the relation of Tensile strentgth vs Elongation of
crosslinked EVA using some crosslinking coagent. (8)
4) EPDM
EPDM is being widely utilized for industrial use based on its excellent
properties on heat resistance and weathering. In application field
being required severe physical properties, peroxide crosslinking in
employed. TAIC® preferably contributes to promote crosslinking rate
and also to improve its heat resistance, compression set and abrasion
resistance.
| Table
2 - Example of Compounding of CPE |
| Formulation |
ELASLEN
401A |
ELASLEN
TR |
| ELASLEN*1
401A |
100 |
|
| ELASLEN*1
TR |
|
100 |
| Barium
Sulfate |
30 |
30 |
| Titanium
Dioxide |
25 |
25 |
| Calucium
Silcate |
25 |
25 |
| Chlorinated
Paraffin |
10 |
10 |
| Paraffin
Wax (Antioxdant) |
3 |
3 |
| TAIC® |
3 |
3 |
| Perhexa
2,5B-40*2 |
5 |
5 |
| Moony Viscosity
ML1+4 121 °C |
68.5 |
37.5 |
| Tensile
Properties |
|
|
| 100%
Modulus (kg/cm2) |
25 |
22 |
| 300%
Modulus (kg/cm2) |
106 |
95 |
| Tensile
Strength (kg/cm2) |
190 |
148 |
| Elongation
(%) |
450 |
470 |
| Hardness
Hs |
60 |
60 |
| Compression
Set (100°C, 70 hrs) (%) |
20.7 |
16.7 |
|
Elongation Change in Chemicals (Room Temp, 14 days) (%) |
|
|
| Nonionic
Soap |
± 0 |
± 0 |
| Ammonia
Water 26% |
± 0 |
± 0 |
| Acetic
Acid 90% |
-20 |
- 15 |
| Hydrogen
Peroxide 10% |
±
0 |
- 6 |
| Sodium
Hypochlorite 13% |
- 5 |
- 10 |
| Nitric
Acid 40% |
- 2 |
- 5 |
| Hydrochloric
Acid 35% |
±
0 |
- 2 |
| Sulfuric
Acid 50% |
- 7 |
- 4 |
| Volume Change
in Oil (100% , 70 hrs) (%) |
|
|
| ASTM
#1 |
- 3.0 |
±15.7 |
| ASTM
#2 |
+ 14.8 |
+ 41.2 |
| ASTM
# 3 |
40.1 |
+ 70.0 |
| Charge in
Heat Ageing (100°C, 98 hrs) |
|
|
| Tensile
Strength (%) |
- 5 |
+ 3 |
| Elongation
(%) |
-
7 |
-
6 |
| Hardness
(Point) |
+ 3 |
+ 3 |
*1: CPE/SHOWA
DENKO CO., LTD.
*2: 2,5-dIMETHYL 2,5 - di-(t-buryl peroxy) hexane (40%) |
|
| Fig. 7 Effect of Crosslinking
Coagents on Peroxide Vulcanization of EVA |
 |
| Formulation: |
| EVATHLENE 410 |
100 PHR |
| Stearic Acid |
1 |
| HAF Carbon |
50 |
| Zinc Oxide |
5 |
| Dicumyl Peroxide |
1 |
| Coagent |
1/270 mol. |
| Vuylcanization, Condition
|
180°C X 10 min |
|
5) Fluoroelastomer
TAIC® is necessarily used for crosslinking reaction of Fluoroelastomer.
TAIC® is employed often for radiation crosslinking coagent for specified
application field of high quality insulating material.
Table 3 is an example of crosslinking of Fluoroelastomer using TAIC®.
(9)
6) Urethane Rubber
TAIC® is effective to improve of crosslink density in the vulcanization
of millable type polyurethane.
B. Polymerization Comonomer
The copolymerization of bi-functional monomer with TAIC® provides a
copolymer crosslinkable by pendant allyl groups in TAIC® unit. Copolymer
having higher concentration of TAIC® unit, provide a thermosetting
characteristic. The copolymerization will result the improved properties
of resistance to heat and weathering and mechanical strength.
1) Emulsion Copolymerization
In emulsion copolymerization of acrylic ester with TAIC®provides an
unique copolymer which has much improved properties including heat,
weathering and inmpact resistance and it is used as a raw material
of acrylic paint and also used as a component for acrylic graft copolymer.
TAIC® can also improve properties of copolymer which is made by emulsion
copolymerization with styrene or acrylonitrile (10)
2) Copolymerization with Thermosetting Polymer
In addition of TAIC® in unsaturated polyester of fiallyl phthalate
prepolymer, heat resistance, hydrolysis resistance and mechanical
strength are much improved. (11)
Fig. 8 shows the Heat Deflection Temperature (HDT) of copolymer provided
by copolymerization of diallyl phtalate prepolymer and TAIC®.
3) Photopolymerization
TAIC® can rapidly react with poly-thiol compounds by ultraviolet light
to provide tightly crosslinked polymeric system. (12) TAIC® can be
participated in the photopolymerization of epoxy acrylates. (15)
| Fig 8. Effect of TAIC® on HDT of Diallyl
Phthalate Polymer |
|
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| Handling
Information |
| Packaging
of TAIC® |
| 20 kg and
200 kg Drum |
| Toxicity
of TAIC® |
| Acute Oral
Toxicity |
Ld 50 (mouse)
666 mg/kg (14) |
| Acute
Toxicity to Orange-red Killfish (15) |
LC50, 48
hrs 275 mg/l |
| LC50, 96
hrs 238 mg/l |
| Mutagenic
Potential |
None (16) |
| Skin Irritation |
None (17) |
| Eye Irritation
|
None (18) |
| Care
in Handling and Storage of TAIC® |
TAIC® has almost no toxicity,
however, it is recommended that gloves and safety goggles
be worn to handle it. If skin is contaminated by TAIC®,
it must be rapidly washed off.
Since as much as 100 ppn of Di-t-butyl hydroxy toluene
(BHT) is added to TAIC® as a stabilizer, it is recommended
that it be stored in as cool and dark a place as possible.
As TAIC® might become solidified in winter, it should be
stored in a warm room or melted with warm water at a temperature
of 35° - 50°C.
In case of removal from TAIC® drums for analyzing, you
must warm up the drums with hot water (35° - 50°C)
until TAIC® becomes liquid with no crystals present, and
stir well before removing. |
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