第四章 實驗結果與討論
壓力參數實驗數據如表 4- 5 所示，分別在 140、200、250、300 bar 下進行，分 析結果如下
B. Camera Window Installation:
Fig. 3-1 Schematic diagram of the experimental apparatus
Fig. 3-1 Schematic diagram of the experimental apparatus 1：CO2 cylinder
2：Pressure gauge
3：Two way needle valve 4：Molecular sieve
5：Cooling water circulation 6：CO2 pump
7：Pressure release valve 8：Back pressure regulator 9：Check valve
10：HPLC pump
11：Three way needle valve 12：Camera Window
13：Tachmeter 14：Safety head 15：Thermocouple 16：Pressure transducer 17：Thar reactor 18：Computer monitor
Fig. 3-2 Schematic diagram for the preparation of P(MEO2MA-co-OEGMA) 將反應物MEO2MA 和 OEGMA
以特定比例放入反應器
打入二氧化碳達所需壓力後，將 起始劑AIBN 打入反應器，開始
進行反應並計算時間
Heating to setting temperature, 70℃
Cooling and depressurization
將蒐集瓶中的乙醇溶液與產物 混合後，取出乙醇溶液
Products
Ethanol evaporation in vacuum oven at 40℃
Fig. 3-3 Schematic diagram for the preparation of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA)
將反應物MEO2MA、OEGMA 和PDMS-g-PAA，起始劑 AIBN，交聯劑 Bis 一起放入反
應器
Pressurization by CO2
加熱反應器至所需溫度和壓力 後開始反應，並紀錄反應時間
Cooling and depressurization
加入去離子水與反應後的產物 混合，在超音波震盪槽中震盪
20min
Centrifuge at 5000rpm for 20 min
抽取離心試管中的上層澄清液 Repeat for 5 times
Dry in vacuum oven at 40℃
Products
Fig. 4-1 Schematic diagram for the polymerization of P(MEO2MA-co-OEGMA) in
P(MEO2MA-co-OEGMA) OEGMA
3850 3500 3150 2800 2450 2100 1750 1400 1050 700
Wavenumber (cm-1)
-O-C=O
R-CH3
C=C peak disappear Fig. 4-2 IR spectra of monomers
(a) MEO2MA (b) OEGMA
Fig. 4-3 IR spectra of P(MEO2MA-co-OEGMA) with 10 mole% OEGMA
3850 3500 3150 2800 2450 2100 1750 1400 1050 700
C=C
-O-1296
C=C
Absorbance(a.u.)
Wavenumber(cm-1) (a)
Fig. 4-4 The phase transition of P(MEO2MA-co-OEGMA) water solution, 10mole% OEGMA
(a) 35℃ (b) 40℃
Fig. 4-5 Comparison of the heating and cooling process at 665 nm observed for the temperature-sensitive property of P(MEO2MA-co-OEGMA) water solution with 10 mole% OEGMA
(a) (b)
20 25 30 35 40 45 50 55
0 20 40 60 80 100
Transmittance (%)
Temperature (oC)
heating cooling
20 30 40 50 60
Temperature(oC) (1) (2)
Temperature (oC) (2)
Fig. 4-6 The effect of solution concentration of P(MEO2MA-co-OEGMA) on temperature-sensitive property
(1) 20 mole% OEGMA, 6 mg/mL (2) 20 mole% OEGMA, 3 mg/mL
Fig. 4-7 The effect of reactants compositions on LCST
(1) 0 mole% OEGMA (3) 10 mole% OEGMA
Fig. 4-8 Comparison of experimental data in this study with the ideal LCST regression line
0 5 10 15 20 25
20 25 30 35 40 45 50 55
reference data (Lutz, 2008) experimental data
Transmittance (%)
Temperature (oC)
Fig. 4-9 The UV analysis for the effect of reaction time on temperature-sensitive property (A) 2hr (B) 3hr
40 45 50 55 60
0 20 40 60 80 100
T (oC)
B
40 45 50 55 60
0 20 40 60 80 100
Transmittance(%)
T(oC)
A
Fig. 4-10 Thermogravimetric curves of P(MEO2MA-co-OEGMA) which have 5 mole% OEGMA in different isothermal times at T = 100 ℃ (1) 0 min (2) 30 min (3) 60 min
100 200 300 400 500 600
0 20 40 60 80 100
100 120 140 160 180 200 220 240
80 85 90 95 100 105
(1) (2) (3)
Weight %
T(OC)
Si
P(MEO2MA-co-OEGMA)
Bis
PDMS-g-PAA-g-P(MEO2MA-co-OEGMA)
Fig. 4-11 Schematic diagram for crosslinking reaction of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) in scCO2
3850 3500 3150 2800 2450 2100 1750 1400 1050 700
Absorbance (a.u.)
Wavenumber (cm-1)
1260
Fig. 4-12 IR spectra of PDMS-g-PAA
Fig. 4-13 The IR spectra of (1) PDMS-g-PAA
(2) P(MEO2MA-co-OEGMA)
3850 3500 3150 2800 2450 2100 1750 1400 1050 700 0.00
Wavenumber(cm-1)
Si-O
3850 3500 3150 2800 2450 2100 1750 1400 1050 700 0.0
0.1 0.2 0.3
Absorbance(a.u.)
Wavenumber(cm-1)
(1) (2)
100 200 300 400 500 600 700 800
0 20 40 60 80 100
(3) (4) (2)
Weight (%)
Temperature (oC) (1)
Fig. 4-14 The IR spectra of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) with different contents of PDMS-g-PAA
(1) 0.154 g PDMS-g-PAA (2) 0.23 g PDMS-g-PAA
Fig. 4-15 Thermogravimetric curves of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) with different compositions (wt%) of PDMS-g-PAA
100 nm 100 nm
Fig. 4-16 The TEM images of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA)
(a)(b)×80000 in acetone (c)(d)×120000 in acetone (e)(f)×80000 in water
(e)
swelling
core
shell
200 nm 200 nm 200 nm
200 nm 100 nm100 nm
200 nm
200 nm 200 nm200 nm
(a)
(b)
(c)
(d)
(e)
(f)
shell
core core shell
swelling
Fig. 4-17 The UV curves of the solution of (PDMS-g-PAA)-g-P(MEO2MA-co- OEGMA) with 30 wt% PDMS-g-PAA at different temperatures (1) 18℃ (2) 20℃ (3) 25℃ (4) 30℃ (5) 35℃
(6) 40℃ (7) 45℃ (8) 50℃ (9) 55℃ (10) 60℃
Fig. 4-18 Determine the LCST value of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) with 30 wt% PDMS-g-PAA by UV analysis at 191 nm
15 20 25 30 35 40 45 50 55 60 65
Temperature (oC)
190 191 192 193 194 195
0.49
Fig. 4-19 Schematic illustration of the relationship between absorbance and temperature Light source
Light source I0
I0
I2
T > LCST Heating
A1= logI0/I1
A2= logI0/I2
I1
T < LCST
I2
Temp , Result：I2<I1ÆA2>A1
Fig. 4-20 The swelling ratio tests for (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) in buffer solutions with various pH values
2 4 6 8 10 12
0.5 1.0 1.5 2.0 2.5 3.0
Swelling Ratio(g/g)
pH value
3850 3500 3150 2800 2450 2100 1750 1400 1050 700
Absorbance (a.u.)
Wavelength (cm-1)
PDMS-g-PAA (1)
(2)
Fig. 4-21 IR spectra of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2 at different temperatures, P = 300 bar for 8 hr (1) 60℃ (2) 70℃ (3) 80℃ (4) 90℃ (5) 100℃
3850 3500 3150 2800 2450 2100 1750 1400 1050 700
Wavenumber (cm-1)
-O-Si-CH3
(3) (5)
(4)
2 4 6 8 10 12 0
4 8 12 16
Swelling Ratio (g/g)
pH value (1)
(2)
2 4 6 8 10 12
0 1 2 3 4
pH value (3)
(4) (5)
Fig. 4-22 The SR tests in buffer solutions with various pH values for (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2
at different temperatures, P = 300 bar for 8 hr (1) 60℃ (2) 70℃ (3) 80℃ (4) 90℃ (5) 100℃
82
Fig. 4-23 SEM images of (a) PDMS-g-PAA and
(PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2 at different temperatures, P = 300 bar for 8 hr
(b) 60℃ (c) 70℃ (d) 80℃ (e) 90℃ (f) 100℃
(b)
(c)
(a) (d)
(e)
(f)
3850 3500 3150 2800 2450 2100 1750 1400 1050 700
Absorbance
Wavenumber (cm-1) (4)
Swelling Ratio (g/g)
pH value (1)
(2) (3) (4)
Fig. 4-24 IR spectra of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2 at different pressures, T = 100 ℃ for 8 hr
(1) 140 bar (2) 200 bar (3) 250 bar (4) 300 bar
Fig. 4-25 The SR tests in buffer solutions with various pH values for
(PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2 at different pressures, T = 100 ℃ for 8 hr
(1) 140 bar (2) 200 bar (3) 250 bar (4) 300 bar
Fig. 4-26 SEM images of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2 at different pressures, T = 100 ℃ for 8 hr
(a) 140 bar (b) 200 bar (c) 250 bar (d) 300 bar
(b)
(c) (a)
(d) (b)
(c)
3850 3500 3150 2800 2450 2100 1750 1400 1050 700
(5)
(4)
(3)
(2)
Wavenumber (cm-1) (1)
Swelling Ratio (g/g)
pH value
Fig. 4-27 IR spectra of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2 at 300 bar, T = 100 ℃ for different reaction times
(1) 2 hr (2) 4 hr (3) 6 hr (4) 8 hr (5) 10 hr
Fig. 4-28 The SR tests in buffer solutions with various pH values for
(PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2 at 300 bar, T = 100 ℃ for different reaction times
(1) 2 hr (2) 4 hr (3) 6 hr (4) 8 hr (5) 10 hr
Fig. 4-29 SEM images of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) which reacted in scCO2 at P = 300 bar, T = 100 ℃ for different reaction times
(a) 2 hr (b) 4 hr (c) 6 hr (d) 8 hr (e) 10 hr
(c) (a)
(b) (b)
(c)
(a) (d)
(e)
Fig. 4-30 IR spectra of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) with different compositions (wt%) of PDMS-g-PAA which reacted in scCO2 at P = 300 bar, T = 100 ℃ for 4 hr
(1) 0 wt% (2) 20 wt% (3) 40 wt% (4) 60 wt% (5) 80 wt% (6) 100 wt%
3850 3500 3150 2800 2450 2100 1750 1400 1050 700
(6)
(5)
(4)
(3)
(2)
Absorbance (a.u.)
Wavenumber (cm-1) (1)
Si-CH3
-O-
Fig. 4-31 SEM images of (PDMS-g-PAA)-g-P(MEO2MA-co-OEGMA) with different compositions (wt%) of PDMS-g-PAA which reacted in scCO2 at P = 300 bar, T = 100 ℃ for 4 hr
(a) 10 wt% (b) 20 wt% (c) 30 wt% (d) 40 wt% (e) 60 wt% (f) 80 wt%
(c)
(c) (a)
(f) (b)
(c)
(d)
(e)
(a)
2 4 6 8 10 12
Swelling Ratio (g/g)
pH value PAA)-g-P(MEO2MA-co-OEGMA) with different compositions (wt%) of PDMS-g-PAA which reacted in scCO2 at P = 300 bar, T = 100 ℃ for 4 hr (1) 10 wt% (2) 30 wt% (3) 40 wt% (4) 60 wt% (5) 80 wt%
Fig. 4-33 The SR tests in buffer solutions with various pH values for (PDMS-g- PAA)-g-P(MEO2MA-co-OEGMA) with different compositions (wt%) of PDMS-g-PAA which reacted in scCO2 at P = 300 bar, T = 100 ℃ for 4 hr
Temperature (oC) (1)
(2) (3) (4) (5)
Table 2-1 Some polymers and surfactants that show temperature-induced, reversible phase-separation in aqueous solutions (Hoffman and Stayton, 2004)
Polymers with amide groups Poly(N-substituted acrylamides)
ex: poly(N-isopropyl acrylamide) (PNIPAM) poly(N,N-dimethyl acrylamide) (PDMAAM) poly(N,N-diethyl acrylamide) (PDEAAM) Poly(N-acryloyl pyrrolidine) (PNAPR)
Poly(N-acryloyl piperidine) (PNAP)
Poly(acryl-L-amino acid amides) (PALAAM)
Polymers and surfactants with ether groups PEO-PPO-PEO triblock surfactants
(PEO: polyethylene oxide; PPO: polypropylene oxide) Alkyl-PEO block surfactants
Random (EO/PO) polymers or copolymers ex: poly(MEO2MA-co-OEGMA) Poly(vinyl methyl ether) (PVME)
Polymers with alchohol groups Hydroxypropyl acrylate (HPA)
Hydroxypropyl methylcellulose (HPMC) Hydroxypropyl cellulose (HPC)
Methylcellulose (MC)
Poly(vinyl alcohol) (PVA) derivatives
Table 2-2 Properties of polymers prepared with oligo(ethylene glycol) methacrylates of various lengths (Lutz, 2008)
Table 3-1 The preparation methods of buffer solutions for different pH values Polymer
Properties in Aqueous Environment
Commercial Availability of the Monomer
1. PMMA hydrophobic yes
2. PMEMA slightly hygroscopic yes 3. PMEO2MA LCST~26℃ yes
4. PMEO3MA LCST~52℃ no 5. POEGMA300 LCST~64℃ yes 6. POEGMA475 LCST~90℃ yes
pH value 0.2 M KHP (ml) 0.2 M HCl (ml) 0.2 M PDHP (ml) 0.2 M NaOH (ml) NaCl (g) Total volume (ml)
pH=2.3 125 101.75 0 0 0.27 500
pH=3.77 125 6.575 0 0 1.384 500
pH=6.96 0 0 86.2 0.05 51.086 500
pH=8.12 0 0 86.2 0.05 80.69 500
pH=11 0 0 0.23 0.05 110.69 530
Table 4-1 The experimental conditions about the effect of compositions of reactants and reaction time on temperature-sensitive property
Rotation Rate (rpm)
Reaction time (hr)
A：The reactants only have MEO2MA and OEGMA
B：The reactants include MEO2MA, OEGMA and PDMS-g-PAA
Table 4-2 The experimental conditions for different operating temperatures
Rotation Rate (rpm)
Reaction time (hr)
Table 4-3 Effect of operating temperature on recovery ratio of products Experimental
number Operating
temperature( )℃ Recovery ratio(％)
No.1 60 11.4
No.2 70 14.4
No.3 80 36.4
No.4 90 29.9
No.5 100 30.5
Table 4-4 Effect of operating temperature on particle size and standard deviation
Table 4-5 The experimental conditions for different operating pressures Experimental
Rotation Rate (rpm)
Reaction time (hr)
Particle size (μm)
Standard deviation
No.1 60 Aggregation ×
No.2 70 Aggregation ×
No.3 80 0.285 0.153
No.4 90 0.284 0.129
No.5 100 0.223 0.077
Original PDMS-g-PAA 11.064 4.54
Table 4-6 Effect of operating pressure on recovery ratio of products
Table 4-7 Effect of operating pressure on particle size and standard deviation Experimental
number Operating pressure (bar) Recovery ratio(％)
No.5 300 30.5
No.6 250 28.8
No.7 200 32.9
No.8 140 45
Experimental number
Operating pressure (bar)
Particle size (μm)
Standard deviation
No.5 300 0.223 0.077
No.6 250 0.947 0.312
No.7 200 1.222 0.64
No.8 140 Aggregation 5.285
≒ 2.407
PDMS-g-PAA 11.064 4.54
Table 4-8 The experimental conditions for different reaction times
Rotation Rate (rpm)
Reaction time (hr)
Table 4-9 Effect of reaction time on recovery ratio of products Experimental
number Reaction Time (hr.) Recovery ratio(％)
No.9 10 33.2
No.5 8 30.5
No.10 6 35.5
No.11 4 34.9
No.12 2 32.6
Table 4-10 Effect of reaction time on particle size and standard deviation
Table 4-11 The experimental conditions for different reactant compositions Experimental
number MEO2MA
(g) OEGMA
(mole%)a PDMS-g-PAA
(wt%)b AIBN
(g) Bis
(g) T ( )℃
P
(bar) Rotation Rate
(rpm) Reaction time (hr)
b: wt% of PDMS-g-PAA in the total mixture of MEO2MA, OEGMA and PDMS-g-PAA Experimental
number
Reaction Time (hr)
Particle size (μm)
Standard deviation
No.9 10 0.247 0.127
No.5 8 0.223 0.077
No.10 6 0.218 0.088
No.11 4 0.225 0.093
No.12 2 0.312 0.202
Table 4-12 Effect of reactant compositions on recovery ratio of products
Table 4-13 Effect of reactant compositions on particle size and standard deviation Experimental
number PDMS-g-PAA
(wt%) Recovery ratio
(%) Grafting ratio (%)
No.13 10 18.3 50.5
No.14 20 25.8 35.5
No.11 30 34.9 34
No.15 40 38.1 25.2
No.16 60 44.8 16.5
No.17 80 49.7 10.8
Experimental
number PDMS-g-PAA(wt%) Particle size (μm)
Standard deviation
No.13 10 9.296 3.779
No.14 20 0.39 0.159
No.11 30 0.225 0.093
No.15 40 0.254 0.089
No.16 60 0.146 0.053
No.17 80 0.139 0.05
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