Anionic Synthesis of Liquid

Polydienes and Their Applications

Taejun Yoo* and Steven Henning

October 14, 2009

Contents

Anionic synthesis of liquid polydienes

 Microstructure
 Macrostructure
 Functionalization

Structure and properties

 Microstructure
 Macrostructure

Applications
Liquid polydiene

- Low molecular weight homopolymers or copolymers containing unsaturated carbon-carbon double bonds
- Curing by sulfur or peroxides

Liquid polydiene Elastomer

Molecular weight 1,000-10,000 100,000-1,000,000

Physical state Viscous liquid Solid
Processing Low shear High shear
Polymerization type Batch or semi batch Batch or continuous
Modification Easy Relatively harder
Catalyst cost on product Critical Negligible
Application Additives for rubber Main rubber products
products
Why anionic polymerization?

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)

A variety of different liquid polymers !

Commercial liquid polydienes (anionic)

-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

Synthomer PB Lithene 1k-9k 10-55 OH Maleinization

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

Microstructure Tg (°C) Tm (°C)

Cis 1,4- - 107 2

Trans 1,4- -106 97/145
Isotactic 1,2 -15 128
Syndiotactic 1,2 -28 156
1,2-vinyl* -4 -

* amorphous
Counter ion and initiator concentration effect

Catalyst Cis-1,4 Trans-1,4 1,2 Lithium catalyst

Lithium 35 52 13
 soluble in hydrocarbon solvents
Sodium 10 25 65
 the lowest 1,2-vinyl content
Potassium 15 40 45
Rubidium 7 31 62  good low temperature properties
Cesium 6 35 59

Initiator Concentration (M) 1.4-Cis (%) 1,4-Trans (%) 3,4-Vinyl (%)*

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

80 (RLi)n n RLi R-, Li+

aggregated Contact ion pair
1.2-vinyl (%)

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)

Polybutadiene with the highest 1,2-vinyl can be prepared in polar solvent

at lower reaction temperature
Comonomer effect (random copolymerization)

-Adding polar additives

-Maintaining the concentration of comonomer with a lower monomer
reactivity ratio high during the copolymerization.


80 

Normalized vinyl (%)

75 Li
70 LB
65
60
55
50
45
40
0 5 10 15 20 25 30 35 40 45 50

Incorporated styrene (%) Li

LB
Effect of styrene content on 1,2-vinyl formation in styrene-butadiene copolymerization

The presence of styrene in copolymerization results in less 1,2-vinyl content

than BD homopolymerization due to steric effect between allylic chain end
and styrene unit.
Cyclization of polybutadiene
High 1,2-vinyl Propagation Linear polybutadiene
 Lewis base
 Reaction temperature

+
Monomer starving condition TMEDA
Vinyl cyclopentane
Cyclization or
 Batch vs. Continuous
 Monomer feed rate

Divinyl cyclohexane

G. Quack and L. J. Fetters, Macromolecules, 11, 369 (1978).

Effect of monomer feed rate

100

80
1,2-vinyl (%)

60 Total 1,2-vinyl

40 Cyclic vinyl

20

0
0 2 4 6
Monomer feed rate (g/min)

Cyclization is favorable in monomer starved reaction condition

Cyclization consumes 1,2-vinyl

Cyclization of polybutadiene (continuous system)

Effect of polar additive Effect of reaction temperature

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

Polar additive/NBL Temperature (c)

Cyclization reaction increases as

 polar additive amount increases (higher 1,2-vinyl)
 reaction temperature increases (Ea cyclization>Ea propagation)
Cyclization of polybutadiene
Effect of cyclic vinyl on T g
Total 1,2-vinyl Cyclic vinyl
-10
15 20 25 30
76 18
-14
76 26

Tg (°C)
-18
77 29

-22

-26
Cyclic vinyl (%)

Effect of cyclic vinyl on viscosity

Stiff structure increases Tg
160,000
Logh ~ (T-Tg)-1
Viscosity @45 (cps)

120,000

Cyclic vinyl has more

80,000
impact on the physical
properties than 1,2-vinyl 40,000

0
15 20 25 30
Cyclic vinyl (%)
Macrostructure

Molecular weight (gram of monomer/moles of initiator)

Molecular weight distribution (Ki >Kp, Xw/Xn=1+1/Xn)

Branched structure (linking reaction and transmetallation)
Chain transfer reaction
1) Initiation and chain transfer
R' Promoter
RLi + R R + PhCH2Li
Li
toluene
R'=H or CH3

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

Ea chain transfer > Ea propagation

 thermodynamic control

 kinetic control

Not applicable for functionalized polymer

Cost reduction of liquid polymer production

Chain transfer reaction
265.45

212.36 Mn calculated: 6,830

Mn measured : 6,120 PI: 1.57
159.27

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

Chain transfer reaction in lithium initiated anionic polymerization increases as

 size of counter ion increases (Li < Na <K )
 polar additive amount increases (Li)
 reaction temperature increases (Ea chain transfer >Ea propagation)
 monomer feed rate decreases
and
 chain transfer reaction is maximized in pure toluene
Branched polymer

[h]b < [h]l

 # of branch

 Length of branch

 MW of backbone

 Type of branch (star, graft and hyper branched)

Reduction in melt and solution viscosities

Processing benefits, applications

Branched polymers by linking reactions

Chlorosilane

SiCl4 + 4 PLi SiP4 + 4LiCl

Divinylbenzene
DVB core
+ * * **
* * ** * *
* = reactive chain end

Epoxy and silanol compounds

PLi + P-OH

OH
OH
OH OH OH OH
OH

Quirk and Zhou US patent 7,235,615

Functionalization

Chain end functionalization

Post polymerization modification
(Functional groups are randomly distributed on polymer backbone)
Chain end functionalization

Functional agent
O
H3O
PCH2CH2OH
PLi +
CO2 H3O
PCOOH

Protected functional initiator or agent

- or w-functionalized polymer by deprotection

Difunctional initiator O
H3O
HO-PB-OH (HTPB)
n BD
Na
CO2 H3O
HOOC-PB-COOH (CTPB)
Post polymerization modification

Hydrogenation (thermal stability and copolymer)

CH 3 CH3
H2
CH 2 C CH CH 2 CH 2 CH CH 2 CH 2 1,2 > 1,4
n n
Polyisoprene Poly(ethylen-co-propylene)

Epoxidation
O
RCO3H
x y x-z y z 1,4 > 1,2

Maleinization

H 1,4 > 1,2

• Esterification
• Addition of acryl group
• Imidization
O O O
O O O
Structure-Property Relationships
Molecular weight effect

Properties that depend on entanglement

Properties that depend on chain ends

Molecular weight Molecular weight

Intermolecular interaction
Entanglement
Number of end groups

Mw Mn

Melt viscosity Tensile strength

h=KMwa Flexural modulus

Izod impact resistance Tg and Tm

Viscosity
Macrostructural (MW) effect

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

J. T. Gruver and G. Kraus, J. Polym. Sci. Part A, 2, 797 (1964)

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).

Viscosity of liquid polydiene is dependant on MW as well as

microstructure:

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

Functional group effect

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 (%)

Tg as a function of oxiran content for a series epoxidized liquid polybutadienes.

 Crosslinking
H H H
H2 H2
Microstructure (1,2- vs. 1,4) C
H
C
H
C C C C C

H H CH
H2C
Macrostructure

Sulfur crosslinking

Molecular weight dependency of crosslinking rate of polyisoprene

Mc of diene elastomers: ~ 12,000 g/mol

Liquid polydienes do not form elastically effective crosslinks

Mizuho Maeda, RubberChem 2006

 Applications
Functional additives
Low viscosity (processing)
Similar chemical properties of elastomers (vulcanization)
Outstanding properties (High thermal stability, good moisture and chemical
resistance, good adhesive characteristics and excellent electrical
properties)
Unfunctionalized liquid polydienes
Processing aids
Low viscosity, non-toxic, low volatility and no bleeding (miscible with rubbers and non-

extractable)

Coagents
1,2-polybutadiene for peroxide cure of elastomers

Wire and cable applications (better heat aging, fluid resistance and electrical properties)

Engineering rubber products (belts, hoses, gaskets and rollers)

Coating and potting agents

Autoxidation with baking or metallic driers (high level of unsaturation)

Tire application
HVPB and SBR: wet traction

LVPB: wear, low temperature properties

Functionalized liquid polydienes

Propellant binder: HTPB and CTPB

Adhesion promoters: Maleinized PB

Polyurethanes: HTPB

Epoxy resin modification: HTPB and CTPB

UV curing: Deoxidized, acrylated PB

Nanocomposite

Polymer-filler interaction
Summary

The microstructure and macrostructure affect the Tg and bulk viscosity

of final diene resin products.

Lithium-based anionic polymerization provides liquid polydienes with a

variety of microstructure and macrostructure including
functionalization.

The unique characteristics of liquid polydiene products has led to their

utility in a wide variety of markets and applications such as functional
additives for rubber and other thermosets, modification of
thermoplastics, adhesives, and coatings.
Adhesion Potential - Metal

5 phr coagent

2000

Lap Shear Adhesion (psi)

Brass
1600
Steel

1200

800

400

0
EPDM, Peroxide cure
Control Ricobond 1731
LVPB-MA HVPB-MA
Ricobond 1756

PB-MA adhesion promoters increase adhesive bond strength

Thermoplastic polyurethanes
HTPB / Diisocyanate / Diol chain extender

PU hard elastomeric
domains soft segment

T < Tsoftening

T > Tsoftening

Melt Flow Vulcanizate

Adhering a Urethane component to a Rubber Compound substrate

 Diene-segments interpenetrate and co-cure with rubber compound
 Urethane segments bond to similar structure in PU

Functional Additive to a traditional Rubber Compound

 varied loading increases impact on physical properties
 impart modulus while minimizing hysteresis (vs. TPE)
 realize advantages from phase structure at higher loading
Nanocomposite
+

Layered clay Polymer

Intercalated nanocomposite Exfoliated nanocomposite

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):

Na+-CLAY + HO2C-R-NH3+Cl- .HO2C-R-NH3+-CLAY + NaCl

Mechanical and thermal properties

Permeability

Flame retardance

UV resistance