È¿ ÁØ 20111128 É Ç

Solid-State Polymerization of Bioplastics
Young Jun Kim Organic-Inorganic Nano Hybrid Material Lab.

http://nhml.hanyang.ac.kr http://sfrl.kist.re.kr
Supercritical Fluid Research Laboratory
Contents
Bioplastics Solid State Polymerization (SSP) BPA-PC (bisphenol A polycarbonate) PTT (poly(trimethylene terephthalate)) HTN (high temperature nylon)
Bioplastics
Solid State Polymerization (SSP)

SSP procedure
Sweep fluid out
Low molecular weight prepolymer
- Synthesize prepolymer - Heat the prepolymer between Tg and Tm - Flow sweep gas
SSP advantages
- Energy-saving process ; low reaction temperature - Green process ; no use of additive reagents - Easy process ; simple procedure - High quality, high molecular weight polymer
Commercially used process

High molecular weight polymer
Sweep fluid in
- Polycarbonate (PC) - Polyester (PET, PTT, PBT) - Polyamide (Nylon)
SSP mechanism
H 2O O
H 2O
N H2
OH H 2N
Stage1
Stage2
Stage3
Stage4
Stage1 : Prepolymers diffuse towards each other

Stage2 : Prepolymer ends react Stage3 : Byproduct(H2O) diffuses through polymer to polymer surface Stage4 : Byproduct diffuses away from polymer surface
Influencing factor of SSP

Reaction condition
- SSP temperature
- SSP time - reactor design - sweep flow
(sort, rate, co-sweep flow)

Prepolymer characteristics - particle size
- molecular weight
- end group ratio - crystallinity - catalyst
- constituents
Apparatus
Melting polymerization
Low temperature SSP
High temperature SSP
Automatic polymerization system for high temperature nylon
Apparatus
High temperature SSP apparatus using a mixture sweep fluid
Effects of sweep flow rate (external diffusion)
Effect of nitrogen flow rate on intrinsic viscosity evolution during SSP of PTTP3 at 190 .
Effect of nitrogen/steam (2/1 volume ratio) flow rate on intrinsic viscosity evolution during SSP of PAP1 at 260 .
Effects of particle size (internal diffusion)
Effect of pellet size on the SSP rate of the PTT prepolymer with an IV of 0.56 dL/g at 210 reported by Duh.
Effect of particle size on intrinsic viscosity evolution during SSP of PTTP3 at 190 .
Exception (internal diffusion)
Effect of particle size on intrinsic viscosity evolution during SSP of PAP1 at 260 .
Effect of moisture
Effect of moisture contents on intrinsic viscosity evolution during SSP of PAP1 at 260 .
Effects of Sweep flow sort (external diffusion)
1. CO2 source 5. SS-316 coil 10. Stirrer
2. Moisture trap 6. Reactor 11. Controller
3. CO2 pump 7,9. Thermocouple
4. Valve 8. Heating bath
Effect of sweep fluid sort on intrinsic viscosity evolution during SSP of PTTP1 at 190 .
BPA-PC poly(bisphenol A carbonate)
Application of BPA-PC
Preparation of prepolymer
SSP of BPA-PC
SSP temperature : 150
Effect of temperature on molecular weight evolution during SSP of PCP1 (crystallinity=11.7%), PCP2 (crystallinity=22.3%), and PCP3 (crystallinity=33.7%).
SSP of BPA-PC
Dependence of crystallinity of polymers solid state polymerized using PCP1 (crystallinity=11.7%), PCP2 (crystallinity=22.3%), and PCP3 (crystallinity=33.7%).
SSP of BPA-PC
Dependence of glass transition temperature on reaction time. PCP1 (crystallinity=11.7%), PCP2 (crystallinity=22.3%), and PCP3 (crystallinity=33.7%)
SSP of BPA-PC
PCP1 (crystallinity=11.7%)
Dependence of the difference between reaction temperature and glass transition temperature of the polymers SSPd.
SSP of BPA-PC
PCP1 (crystallinity=11.7%) PCP2 (crystallinity=22.3%) PCP3 (crystallinity=33.7%)
Melting isotherms for polymers solid state polymerized.
PTT (poly(trimethylene terephthalate))
Poly(trimethylene terephthalate)
Application of PTT
PTT synthesis mechanism
SSP of PTT
PTTP1 (IV = 0.121 dL/g)
PTTP2 (IV = 0.205 dL/g)
PTTP3 (IV = 0.416 dL/g)
Effect of temperature on molecular weight evolution during SSP of PTTP1 (IV = 0.121 dL/g), PTTP2 (IV = 0.205 dL/g), and PTTP3 (IV = 0.416 dL/g).
SSP of PTT
Effect of prepolymer molecular weight on SSP of PTT. PTTP1 (IV = 0.121 dL/g), PTTP2 (IV = 0.205 dL/g), and PTTP3 (IV = 0.416 dL/g)
SSP of PTT
The simple, modified, second-order kinetic model of the SSP rate is expressed by the following equation: = 2 ( )2 (1)
where C is the total end-group concentration, t is the reaction time, ka is the apparent reaction rate constant, and Cai is the apparent inactive end-group concentration. By integration at t =0, equation (1) can be rearranged into the following form: 0 = = 2 (0 ) = 2 (0 ) (2)
where
(3) (4)
Here, a and b are the slope and intercept, respectively, of the straight line obtained from a (C0 -C ) / t versus C plot (see next slide). Cai can be estimated as b/a from equations (6) and (7). ka can be calculated from equation (6) using the known values of a, b , and Cai. Solving for C in equation (5), the following equation is obtained: = 0 + 1 + (5)
Because C is often given in units of mol/g in polyester industries, C can be related to Mn as = 2 106 (6)
The simple, modified, second-order kinetic model of the SSP rate is expressed by the following equation: [ ]=3.13 104 0.80 (7)
Using equations (8)~(10), the intrinsic viscosities in the course of SSP can be estimated by the following equation: []=34.3849
1+ 0 +
0.80
(8)
SSP of PTT
PTTP1 (IV = 0.121 dL/g)
PTTP2 (IV = 0.205 dL/g)
PTTP3 (IV = 0.416 dL/g)
( C0 C ) / t versus C plots for SSP
SSP of PTT
SSP of PTT
Melting isotherms for polymers solid state polymerized using (a) PTTP1 (IV = 0.121 dL/g), (b) PTTP2 (IV = 0.205 dL/g), and (c) PTTP3 (IV = 0.416 dL/g) at reaction temperatures of 170~190 with a fixed reaction time of 6 h. (d) Comparison of melting isotherms for polymers solid state polymerized using PTTP1, PTTP2, and PTTP3 at the fixed temperature of 190 and a fixed reaction time of 6 h.
SSP of PTT
SSP of PTT
Wide-angle X-ray diffraction patterns of PTTP1 and

Dependence of (a) T m and (b) crystallinity of polymers solid state polymerized using PTTP1 (IV = 0.121 dL/g), PTTP2 (IV = 0.205 dL/g), and PTTP3 (IV = 0.416 dL/g) on the reaction time at a reaction temperature of 190 .
Dependence of (a) T m and (b) crystallinity of polymers solid state polymerized using PTTP1 (IV = 0.121 dL/g), PTTP2 (IV = 0.205 dL/g), and PTTP3 (IV = 0.416 dL/g) on the reaction time at a reaction temperature of 180 .
solid state polymerized PTT from PTTP1.
HTN (high temperature nylon)
Applications of HTN
Automobile parts
Electronics
Manufactures of HTN
Preparation of nylon salt
Experimental synthesis conditions and properties of prepolymers
SSP of HTN
2.5
PAP1-MP case1 PAP1 PAP1-MP case2 PAP2 PAP1-MP case3 PAP3
2.0
Intrinsic viscosity (dL/g)
1.5
1.0
0.5
0.0 0 12 24 36 48
Time (hr)
SSP of HTN
Effect of temperature on intrinsic viscosity evolution during SSP of PAP1 (IV = 0.085 dL/g) at 220, 240, and 260 .
Effect of temperature on intrinsic viscosity evolution during SSP of PAP5 (IV = 0.180 dL/g) at 255 and 275 .
SSP of HTN
SSP of HTN
SSP of HTN
SSP of HTN
SSP of HTN
SSP of HTN
SSP of HTN
Thank you for your attention!!!
http://www.hanyang.ac.kr
http://www.kist.re.kr
http://sfrl.kist.re.kr

È¿ ÁØ 20111128 É Ç

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Solid-State Polymerization of Bioplastics

Young Jun Kim Organic-Inorganic Nano Hybrid Material Lab.

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

Solid State Polymerization (SSP)

Low molecular weight prepolymer

Commercially used process

- Polycarbonate (PC) - Polyester (PET, PTT, PBT) - Polyamide (Nylon)

Supercritical Fluid Research Laboratory

Stage1 : Prepolymers diffuse towards each other

Supercritical Fluid Research Laboratory

Influencing factor of SSP

(sort, rate, co-sweep flow)

Low temperature SSP

High temperature SSP

Automatic polymerization system for high temperature nylon

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

Effects of sweep flow rate (external diffusion)

Supercritical Fluid Research Laboratory

Effects of particle size (internal diffusion)

Supercritical Fluid Research Laboratory

Exception (internal diffusion)

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

Effects of Sweep flow sort (external diffusion)

1. CO2 source 5. SS-316 coil 10. Stirrer

2. Moisture trap 6. Reactor 11. Controller

3. CO2 pump 7,9. Thermocouple

4. Valve 8. Heating bath

Supercritical Fluid Research Laboratory

BPA-PC poly(bisphenol A carbonate)

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

SSP temperature : 150

SSP temperature : 170

SSP temperature : 190

Supercritical Fluid Research Laboratory

SSP temperature : 150

SSP temperature : 170

SSP temperature : 190

Supercritical Fluid Research Laboratory

SSP temperature : 150

SSP temperature : 170

SSP temperature : 190

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

Melting isotherms for polymers solid state polymerized.

Supercritical Fluid Research Laboratory

PTT (poly(trimethylene terephthalate))

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

PTT synthesis mechanism

Supercritical Fluid Research Laboratory

Supercritical Fluid Research Laboratory

PTTP1 (IV = 0.121 dL/g)

PTTP2 (IV = 0.205 dL/g)

PTTP3 (IV = 0.416 dL/g)

Supercritical Fluid Research Laboratory

SSP temperature : 170