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STUDIES IN FLAME RETARDANT COATINGS
Presented by
Kunal D. WazarkarM.Tech in Surface Coating Technology
Research Supervisor
Dr. Anagha S. Sabnis
2
INTRODUCTION NEED OF FLAME RETARDANTS????
3
FLAME RETARDANTS??
Flame retardants are the chemicals used in thermoplastics, thermosets, textiles and coatings to inhibit or resist the spread of fire.
Two ways to achieve flame retardancy:
Additive Route Reactive Route
Physical incorporation of flame retardants
Chemical modification of polymer backbone with flame retardants
High concentration of flame retardants
Low concentration of flame retardants
Problems of phase separation, high viscosity
No such issues
4
OBJECTIVES OF THE RESEARCH To synthesize phosphorous containing flame
retardants having multiple functionalities and incorporate them in polymer backbone through reactive modification.
To modify polyurethane backbone with Phosphorous containing triol and to develop flame retardant aqueous Polyurethane Dispersions.
To synthesize un-saturation containing phosphorous based reactive flame retardants and incorporate them in unsaturated polyester backbone to prepare flame retardant unsaturated polyester composites.
5
SCHEME-1
Synthesis and Reactive Incorporation of Novel Phosphorous based Flame
Retardant in Polyurethane Dispersions
6
SYNTHESIS OF PHOSPHOROUS TRIOL
Conversion: 91.30 %
PCl
O
Cl
Cl
Phosphorus Oxychloride
HO
HN
N-Methylaminoethanol
P
O
N
N
N
OH
OH
HO
P- Containing Triol
3 0-5 degC
Ice Bath
HCl3
7
CHARACTERIZATION
Hydroxyl value
FTIR Spectroscopy 1H-NMR Spectroscopy 31P-NMR Spectroscopy
Practical Value Theoretical Value
595 mg of KOH/gm of sample
625 mg of KOH/ gm of sample.
8
FTIR SPECTROSCOPYPeaks (cm-
1)Fn group
750 & 948 P-N-C linkage
2951 -CH3
3390 -OH stretching
1463 -CH2
1031 -C-N linkage
1215 -P=O
9
1H-NMR SPECTROSCOPY
Chemical Shift
(ppm)
Protons
3.85 -OH
3.47 & 2.94 -CH2 (methylene
)
2.62 -CH3
10
31P-NMR SPECTROSCOPY
Chemical Shift: 1.94 ppm
11
FORMULATION OF FRPUDS
Raw Materials Mol.wt Eq.wt
No. of Equivalents
Conventional PUD-30 PUD-40 PUD-50
IPDI 222 111 4.4 4.4 4.4 4.4
PEG-400 400 200 1.3 0.91 0.78 0.65
FROH 269 89.67 0 0.39 0.52 0.65
DMPA 134 67 0.7 0.7 0.7 0.7
12
SYNTHESIS OF FR-PUDSStep 1: Synthesis of Urethane Prepolymer
OCN R NCO HO R' OH
COOH
HO OH
OHHO
OH
P
IPDI DMPA PEG-400 P-containing Triol
60-6
5 de
gC
DB
TD
L
COOH
NHCOOOOCHNRR
NHCOOOOCHN
R'
NHCOO
R'
OOCHN
OOCHNOOCHN
OOCHN
P
R
R
NHCOO
ROOCHN
RNCO
NHCOO
P
ROCN
NCO prepolymer
A
13
CONTD..
Step 2: Chain Extension and Neutralization of synthesized PU prepolymer
EDA, 50 degC
Chain ExtensionA
COOH
NHCOOOOCHNRR
NHCOOOOCHN
R'
NHCOO
R'OOCHN
OOCHNOOCHN
OOCHN
P
R
R
NHCOO
ROOCHN
R
NHCOO
P
RNH
NH
NH
C
O
C
O
NH
TEA
Neutralization
OOC
NHCOOOOCHN
RRNHCOOOOCHN
R'
NHCOO
R'
OOCHN
OOCHNOOCHN
OOCHN
P
R
R
HCOON
R
NHCOO
R
NHCOO
P
R
NH
NH
NH
C
O
C
O
NH
NH
COATING PROPERTIESCharacterization Commercial Conventional PUD-30 PUD-40 PUD-50
Gel Content (%) - 70.32 72.64 78.92 85.57
Mechanical Properties
DFT (µ) 40-50 45-55 50-70 50-65 45-60
Cross Cut
Adhesion
5B 4B 4B 4B 4B
Pencil Hardness HB B H 2H 4H
Scratch
Hardness
750g 750 g 1 Kg 1 Kg 1.5 Kg
Impact
Resistance
(lbs.inch)
Extrusion:
Intrusion:
70.86
70.86
70.86
70.86
64.96
47.24
59.05
35.43
47.24
35.43
Flexibility (mm) 0 0 3 3 5
Optical Properties
Gloss@600 55 30 32 37 46
Chemical Properties
Solvent Resistance
MEK <50 <50 <50 <50 <100
Xylene <50 <50 <100 <150 >200
15
THERMO-GRAVIMETRIC ANALYSIS
Samples Tonset (0C) Toffset (0C) Char yield (%)
Conventional 245 390 -
PUD-30 236 450 1.24
PUD-40 230 456 2.70
PUD-50 219 460 3.82
16
PHOSPHOROUS AND NITROGEN CONTENT IN FR-PUDS
Component PUD-30 PUD-40 PUD-50
Phosphorous (wt %) 0.4 0.6 0.8
Nitrogen (wt %) 0.6 0.8 1.0
17
FLAME RETARDANT PROPERTIES
Characterization PUD-30 PUD-40 PUD-50
UL-94 test VTM-1 VTM-0 VTM-0
Conventional PUD PUD-30 PUD-40 PUD-500
5
10
15
20
25
30
35
40
LOI Values
18
CONCLUSION
Phosphorous containing triol has been synthesized and successfully incorporated in PU backbone to yield FRPUDs.
Pencil and Scratch Hardness, Gloss, MEK and Xylene rub resistance, Thermal Stability
Flexibility and Impact resistance
Amount of Flame Retardan
t
19
CONTD..
Order of Flame retardancy PUD-50 (37) > PUD-40 (33) > PUD-30 (29)
Significant increase in LOI value may be attributed to the synergistic effect of phosphorous and nitrogen that has resulted in excellent overall flame retardancy of PU films.
20
SCHEME-2
Flammability Behavior of Unsaturated Polyester Composites Modified with
Un-saturation Containing Phosphorous based Reactive Flame Retardants
21
SYNTHESIS OF TRI-ALLYL PHOSPHATE (TAP)
% Conversion: 88.47 %
PCl
O
Cl
Cl
Phosphorus oxychloride
OH
Allyl alcoholexcess
P
OO
O
O
Triallyl phosphate (TAP)
Ice Bath
0-5 degC
HCl3
22
CHARACTERIZATION
Iodine value
FTIR Spectroscopy 1H-NMR Spectroscopy 31P-NMR Spectroscopy
Theoretical I.V. Practical I.V.
349.26 gm of I2/ 100 gm of sample
315.4 gm of I2/ 100 gm of sample
23
FTIR SPECTROSCOPY
Peaks (cm-
1)Fn group
1465 -CH2 group
1159 -P=O bond
987 -C=C-
776 P-O-C linkage
24
1H-NMR SPECTROSCOPYChemical
Shift (ppm)Protons
5.93 =CH-
5.36 & 5.28 =CH2 (allylic)
4.25 -CH2 (methylene)
25
31P-NMR SPECTROSCOPYChemical Shift: -0.691 ppm
26
SYNTHESIS OF DTAP
PCl
O
Cl
Cl
Phosphorus oxychloride
OH
Allyl alcoholexcess
HOO
OH
Diethylene glycol
2 P
O
Cl
Cl
O OO P Cl
Cl
O
Intermediate
P
O
O
O
OO
O P
O
O
O
Ice bath
0-5 degC
Step 1
Step 2
DEG bridged Tetra-allyl phosphate (D-TAP)
% Conversion: 85.82 %
27
CHARACTERIZATION
Iodine value
FTIR Spectroscopy 1H-NMR Spectroscopy 31P-NMR Spectroscopy
27
Theoretical I.V. Practical I.V.
238.30 gm of I2/ 100 gm of sample
207.12 gm of I2/ 100 gm of sample
28
FTIR SPECTROSCOPY
Peaks (cm-1)
Fn group
1456 -CH2
1180 -P=O bond
975 -C=C-
781 P-O-C bond
1220 C-O-C linkage
1H-NMR SPECTROSCOPY
Chemical Shift (ppm)
Protons
5.93 =CH-
5.38 & 5.18 =CH2 (allylic)
4.32 & 4.2 -CH2 (allylic)
3.74 -CH2 (DEG)
30
31P-NMR SPECTROSCOPY
Chemical Shifts: -0.716 and
-0.741 ppm
FORMULATION OF FRUPR COMPOSITES
Composites UPR (wt%)
Styrene (wt%)
TAP (phr) DTAP (phr)
Commercial
UPR
65 35 -- --
UPR-TAP-5 65 35 5 --
UPR-TAP-10 65 35 10 --
UPR-TAP-15 65 35 15 --
UPR-DTAP-5 65 35 -- 5
UPR-DTAP-10 65 35 -- 10
UPR-DTAP-15 65 35 -- 15
32
SYNTHESIS OF FRUPR COMPOSITES
O
O O
O
P
O
P
O
O
R
O
O
O
O
O
R
O
O
O
R
O
OO
R
P
O
0.02
%C
o-O
c toa
t e
2% M
EK
P
Unsaturated Polyester Styrene P-based flame retardant
Flame retardant Unsaturated Polyester Composites
33
COMPOSITE PROPERTIES Mechanical Properties:
Tensile strength and % Elongation Flexural strength Impact strength Shore D hardness
Thermal Properties: Differential Scanning Calorimetry (DSC) Thermo-Gravimetric Analysis (TGA)
Flame Retardant Properties: Limiting Oxygen Index (LOI) Underwriters Laboratories Testing (UL-94)
34
MECHANICAL PROPERTIES
0 2 4 6 8 10 12 14 1620
22
24
26
28
30
Tensile Strength Vs phr of Flame Retardant
UPR-TAP
UPR-DTAP
phr of flame Retardant
Tensile S
trength
(M
pa)
0 2 4 6 8 10 12 14 160.8
1
1.2
1.4
1.6
1.8
2
% Elongation Vs phr of Flame Retardant
UPR-TAP
UPR-DTAP
phr of Flame Retardant
% E
longati
on
35
0 2 4 6 8 10 12 14 1615
16
17
18
19
20
21
22
23
24
25
Flexural Strength Vs phr of Flame Retardant
UPR-TAP
UPR-DTAP
phr of Flame Retardant
Fle
xura
l Str
ength
(M
pa)
0 2 4 6 8 10 12 14 160.3
0.4
0.5
0.6
0.7
0.8
0.9
Impact Strength Vs phr of Flame Retardant
UPR-TAP
UPR-DTAP
phr of Flame Retardant
Impact
Str
ength
(K
J/m
2)
36
0 2 4 6 8 10 12 14 1666
68
70
72
74
76
78
80
82
84
86
Shore Hardness Vs phr of Flame Retardant
UPR-TAPUPR-DTAP
phr of Flame Retardant
Sh
ore
Ha
rdn
ess
37
THERMAL PROPERTIES
DSC Curves of UPR-TAP Composites
38
DSC Curves of UPR-DTAP Composites
39
THERMO-GRAVIMETRIC ANALYSISUPR-TAP Composites
40
UPR-DTAP Composites
FLAME RETARDANT PROPERTIES
Composites Afterflame
time t1
(s)
Afterflame
time after
second flame
t2 (s)
Dripping
Behavior
UL-94 rating
Commercial
UPR
Flame doesn’t Extinguish
UPR-TAP-5 15 47 Serious
Dripping
V-2
UPR-TAP-10 8 25 No dripping V-0
UPR-TAP-15 3 17 No dripping V-0
UPR-DTAP-5 17 37 No dripping V-1
UPR-DTAP-10 6 22 No dripping V-0
UPR-DTAP-15 2 15 No dripping V-0
UL-94 Testing
42
Limiting Oxygen Index (LOI)
5 10 150
5
10
15
20
25
30
35
LOI Values
TAPDTAP
phr of flame retardant
LO
I V
alu
es
43
CONCLUSION Unsaturated phosphorous containing flame
retardants, TAP and DTAP were synthesized and incorporated in UPR.
The gel content of all composites was found to be in the range of 85%-90%.
Tensile strength, Shore hardness, Tg, Thermal Stability, Flame Retardancy
% Elongation, Flexural strength and Impact strength
Amount of Flame
Retardants
44
ACKNOWLEDGEMENT
My sincere thanks to
Research Guide: Dr. Anagha Sabnis
SAIF Lab, IIT Bombay All the departments of ICT Faculties and non-teaching staff Friends Family
THANK YOU