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Applications
Liquid polydiene
- Low molecular weight homopolymers or copolymers containing unsaturated carbon-carbon double bonds
- Curing by sulfur or peroxides
Microstructure
Polymer composition (styrene, butadiene, isoprene)
Mode of addition (1,4- and 1,2- vinyl or 3,4-vinyl)
Monomer sequence distribution (random, tapered or block)
Cyclic structure (batch vs. semi batch)
Macrostructure
Molecular weight and distribution
Molecular geometry (linear and branched)
Functionalization
In chain
Chain end: mono and difunctional (telechelic)
-Plastikator 32
-Butarez (HTPB and CTPB)
1,2-vinyl Post
Liquid Functional
Producer Trade name MW polymerization
polymer (%) group
Modification
Maleinization
Nippon Soda PB Nisso 1k-4k 85-90 OH, COOH
Hydrogenation
Epoxidation
Ricon 1.5k-8k 20-90
Sartomer PB, SBR Maleinization
Krasol 2k-10k 60-65 OH
Hydrogenation
PB, PI LBR
Kuraray 25-50k - OH, COOH Maleinization
SBR, SIR LIR
Microstructure
Mode of addition (1,4- vs. 1,2-)
Reaction conditions
Comonomer effect in copolymerization
Cyclic vinyl formation
Microstructure of polydienes
R H2C
R
C CH
C CH
CH 2 H2C
R CH 2
Cis-1,4-addition Trans-1,4-addition
Diene H2 H2 R
C C
R=CH3 or H CH C C CH CH
H2
C CH 2
R HC CH 2 H2C
CH 2 Cyclic vinyl
CH
3,4-addition 1,2-addition H2C
* amorphous
Counter ion and initiator concentration effect
6.12x10-2 74 18 8
1.0x10-3 78 17 5
PI
1.0x10-4 84 11 5
0.8x10-5 97 0 3
5x10-1 53 47
PB 5x10-2 90 10
5x10-3 93 7
* 1,2-vinyl for polybutadiene
Polar additive and Temperature effect
60 - +
- +
R // Li R + Li
40 Free ions
30 C
20 70 C
0
Polar solvent
0 0.5 1 1.5
TMEDA/NBL (molar ratio) Presence of Lewis base (alkali metal
alkoxides) in HC solvent
80
Monodendate vs. Bidendate
60
1.2-vinyl (%)
Temperature
40
30 C
70 C
20
0
0 20 40 60 80 100
THF/NBL (molar ratio)
T.A. Antkowiak, A.E. Oberster, A.F. Halasa, and D.P. Tate JPS, Part A-1 Vol. 10, 1319 (1972)
80
Normalized vinyl (%)
75 Li
70 LB
65
60
55
50
45
40
0 5 10 15 20 25 30 35 40 45 50
+
Monomer starving condition TMEDA
Vinyl cyclopentane
Cyclization or
Batch vs. Continuous
Monomer feed rate
Divinyl cyclohexane
100
80
1,2-vinyl (%)
60 Total 1,2-vinyl
40 Cyclic vinyl
20
0
0 2 4 6
Monomer feed rate (g/min)
100 100
80 80
1,2-vinyl (%)
1,2-vinyl (%)
60 Total 1,2-vinyl
60
1,2-vinyl
40 Total 1,2-vinyl 40 Cyclic vinyl
Cyclic vinyl
20 20
0 0
0 2 4 6 8 30 50 70 90
Tg (°C)
-18
77 29
-22
-26
Cyclic vinyl (%)
120,000
0
15 20 25 30
Cyclic vinyl (%)
Macrostructure
2) Propagation
R' R'
R' nBD Li
PhCH2Li + PhCH2 PhCH2
Li n+1
3) chain transfer
R' PhCH3 R'
Li H + PhCH2Li
PhCH2 PhCH2
n+1 n+1
kinetic control
Response
106.18 Mn calculated: 17,750
Mn measured : 1,830 PI: 3.54
53.09
0.00
-53.09
11.8 14.1 16.5 18.8 21.1 23.4
Minutes
# of branch
Length of branch
MW of backbone
Chlorosilane
Divinylbenzene
DVB core
+ * * **
* * ** * *
* = reactive chain end
PLi + P-OH
OH
OH
OH OH OH OH
OH
Functional agent
O
H3O
PCH2CH2OH
PLi +
CO2 H3O
PCOOH
Difunctional initiator O
H3O
HO-PB-OH (HTPB)
n BD
Na
CO2 H3O
HOOC-PB-COOH (CTPB)
Post polymerization modification
Epoxidation
O
RCO3H
x y x-z y z 1,4 > 1,2
Maleinization
Intermolecular interaction
Entanglement
Number of end groups
Mw Mn
10
9
h0=KMwP
High MW 8
7
Log ha
Log h 0
5 P=3.4
Shear thinning
Broad MWD 4
3
P=1
Newtonian Region 2
Low MW 1
0
0 1 2 3 3 3.5
Mcr 4 4.5 5 5.5 6
.
Log shear rate ()
Log Mw
Mcr
Polybutadiene: 6,000
Random coils Oriented coils
Polyisoprene: 10,000
Viscosity
Microstructural effect
90000
LVPB
80000
HVPB
70000 SBR
Viscosity (cps)
60000
50000
40000
30000
20000
10000
0
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Mn (g/mole)
Zero shear viscosity data (Brookfield) as a function of both molecular weight and
microstructure using a series of commercially available liquid polydiene grades
( low vinyl polybutadiene, high vinyl polybutadiene, poly(butadiene-co-
styrene).
high vinyl polybutadienes > SBR copolymers > low vinyl polybutadienes
Viscosity
Functional group effect on chain end functionalized PB
35000
Non-fun
Viscosity at 25 deg C (cP)
30000
Fun
25000
20000
15000
10000
5000
0
0 1000 2000 3000 4000 5000 6000
Mn (g/mole)
Glass transition temperature
Tg = Tg() - (A/Mn)
0
-10 -40
5200
-20
4700
-30 -50
2900
Tg (deg C)
Tg (deg C)
-40
3900 -60
-50
1800
-60
3900 1400 -70
-70
-80 8000
4500 -80
-90 2500
-100
-90
0 20 40 60 80 100
0 20 40 60 80 100
Vinyl (%) Amount of isoprene (%)
Tg as a function of vinyl content and molecular weight for a series of Tg as a function of comonomer content for a series of butadiene-
commercially available liquid polybutadienes. isoprene copolymers.
Glass transition temperature
O
RCO3H
x y x-z y z
-60
-65
-70
Tg (deg C)
-75
-80
-85
-90
0 1 2 3 4 5 6
Oxiran (%)
H H CH
H2C
Macrostructure
Sulfur crosslinking
extractable)
Coagents
1,2-polybutadiene for peroxide cure of elastomers
Wire and cable applications (better heat aging, fluid resistance and electrical properties)
Tire application
HVPB and SBR: wet traction
Polyurethanes: HTPB
Nanocomposite
Polymer-filler interaction
Summary
5 phr coagent
2000
1200
800
400
0
EPDM, Peroxide cure
Control Ricobond 1731
LVPB-MA HVPB-MA
Ricobond 1756
PU hard elastomeric
domains soft segment
T < Tsoftening
T > Tsoftening
An organophilic clay can be produced from a normally hydrophilic clay by ion exchange with an organic
cation such as an alkylammonium ion. For example, in montmorillonite, the sodium ions in the clay can
be exchanged for an amino acid such as 12-aminododecanoic acid (ADA):
Permeability
Flame retardance
UV resistance