NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 奈米化工與高分子材料 2003/11/8 報告人 : 吳逸謨

NCKU-PRLPolym. Res. Lab.Nation Cheng Kung Univ.

奈米化工與高分子材料• 2003/11/8

• 報告人 : 吳逸謨


1950 - 原子彈

1960~70 - 太空登月

原子筆，原子襪，原子褲，原子能， etc

太空被，太空衣，太空鞋，太空纖維 etc


2000 – 奈米奈米水，奈米電鍋，奈米冰箱，奈米冷氣機，奈米 SARS 口罩，奈米塗料，奈米潤滑油，

奈米保養化妝品，奈米 - 米， etc…

奈米中藥，奈米顆粒，奈米管， etc…

奈米生化，奈米醫學， etc


奈米福碳公司 -2003 奈米科技論壇

Dr. Alan MacDirmid – (2002 Chemistry Nobel-Prize Laureate

for conducting polymers)He said Taiwan could someday become a

奈米島


Analyses of Crystal Forms in Syndiotactic Analyses of Crystal Forms in Syndiotactic Polystyrene Intercalated with Layered Nano-Polystyrene Intercalated with Layered Nano-

Clays Clays


高分子 – 超奈米


IntroductionIntroduction

Over the last decade, polymer-layered silicate nanocomposites (PLSNs) with nano-scale reinforcements have been the focus of extensive study.

Incorporation of the organo-layered silicates into the polymers results in enhanced mechanical strength, improved thermal stability and flame retardancy, increased solvent resistance and barrier properties, higher ionic conductivity, reduced thermal expansion coefficient, and controlled biodegradability.

Dispersivity of the clay particles plays the pivotal role to influence the ultimate properties of the PLSNs. For a typical polymer, the key factors of the clay dispersion are the method of synthesis, structure of the intercalant (generally onium surfactants) and concentration of clay.


sPS is a semi-crystalline polymer exhibiting complex polymorphic behavior with multiple melting characteristics.

The main objectives of the present investigation are:

(1) to elucidate the multiple melting characteristics of sPS/clay nano-composites vs. conventional micro-composites by comprehensive thermal and X-ray diffraction evidence;

(2) (2) to investigate the effect of Tc on the relative ratio of the polym

orphic sPS crystals in presence of pristine and organo-clays; and

(3) (3) to depict the spherulitic morphology of sPS as affected by incorporation of different kind of clays.

ObjectivesObjectives


ExperimentalExperimental

Syndiotactic polystyrene (sPS)Syndiotactic polystyrene (sPS) (Idemitsu Petrochemical Co., Ltd., Japan)Mw =210 kg/mol

CloisiteCloisite®® Na+ (Na-MMT) Na+ (Na-MMT) (Southern Clay Product Inc., USA)CEC = 92.6meq/100g clay (d001 = 11.7Å), sp.gr. = 2.86

Cloisite® 10A (Clay-10A) (Southern Clay Product Inc., USA)

Modifier : 2MBHT(dimethyl, benzyl, hydrogenatedtallow, quaternary ammonium salt) Modifier conc. = 125meq/100g clay (d001 = 19.2Å), sp.gr. = 1.90

HT is Hydrogenated Tallow (~65% C18; ~30% C16; ~5% C14)

• 1,1,2,2-tetrachloroethane (TCE) (Showa Chemicals Inc., Japan) ( = 19.8 MPa½, b.p. 145oC, 1.6 g/cc)

N

CH3

CH3

HT

H2C+

Materials UsedMaterials Used


Experimental (contd.)Experimental (contd.)

Differential Scanning Calorimetry (DSC): DSC-7 (Perkin-Elmer) attached with cooling

accessory Intracooler 2 (Perkin-Elmer).

Wide-Angle X-ray Diffraction (WAXD): Shimadzu XRD-6000 with Cu Kα radiation (30

kV and 40 mA) and a wavelength of 1.542 Å. The scanning 2θ angle ranged between 2° a

nd 30° with a step scanning rate of 2°/min.

• Transmission Electron Microscopy (TEM): JEOL JEM 1200-EX TEM. Epoxy-mounted

samples were ultra-microtomed with a diamond knife on a Leica Ultracut R microtme (n

ominal thickness of 50~70 nm). The sections were transferred from water to carbon coate

d 200-mesh Cu grids.

• Polarized Optical Microscopy (POM): Nikon Optiphot-2, POL equipped with UFX-DX a

utomatic exposure. Linkam THMS-600 with TP-92 temperature programmer was used a

s microscopic heating stage.

InstrumentationInstrumentation


Solvent used - 1,1,2,2-tetrachloroethane (TCE)

Solution was stirred for 1h at 130oC to dissolve sPS (2-wt%)

Clay (vacuum dried at 80oC for 6h) was added into the polymer solution

Clay suspension was vigorously stirred at 60oC in oil bath for 24h

The resultant solution was cast as thin film at 60 oC for 24h

Residual solvent was removed by vacuum drying at 110 oC for 7 days

Cast film was grounded to fine powder

Powdered samples were further dried at 110 oC for 3 days for complete

removal of solvent

Solution Intercalation of sPSSolution Intercalation of sPS


Composition

Tg (C)

Tcc (C)a

Tm (C)

Hm (J/g)b

sPS (neat)

89.6

154.0

269.7

28.8

sPS + Na-MMT (5%)

90.4 152.0 268.3 26.6

sPS + C10A (5%) 86.3 147.7 267.7 19.6

sPS + C10A (10%)

58.6 137.3 244.3 14.0

All the samples were melted at 290 C for 10 min to remove all the crystalline forms and then quenched by liquid nitrogen to obtain the amorphous state (DSC scan rate = 20°C/min)

a Tcc: peak temperature of cold crystallization. b Hm: melting enthalpy.

Thermal transitions of sPS/clay-HybridsThermal transitions of sPS/clay-Hybrids


4 6 8 10

2

Inte

nsit

y (a

.u.)

(a) Na-M MT(b) C10A(c) s-PS (neat)(d) s-PS + Na-MMT(5% )(e) s-PS + C10A(5% )(f) s-PS + C10A(10% )

(a)

(b)

(c)

(d)

(e)

(f)

Dispersion of layered silicates in sPS Dispersion of layered silicates in sPS No peak in the relevant range (2 = 3 ~ 8) for

neat sPS. A broad peak around 2 9.2 indicates the existence of -crystal form in this

TCE-cast sPS matrix (Trace c)

Peak at 2 6.1 in sPS/Na-MMT (5-wt%)

composite indicates the presence of clay-induced

-crystals of TCE-cast sPS overlapped by the d001

peak of the unintercalated Na-MMT (Trace d)

No significant XRD peak in the region of 2 =

3-5 sPS/ C10A (5-wt%) nanocomposite,

indicating successful intercalation of sPS into the

silicate layers (Trace e)

Small and broad peak at 2 6 for C10A (10-

wt%) nanocomposite suggests the presence of -

crystal of sPS in the cast sample, still no peak in

the region of 2 = 3-5 (Trace f)

d001 1.17 nm

d001 1.88 nm


TEM images of sPS/clay-HybridsTEM images of sPS/clay-Hybrids

sPS/Na-MMT(5-wt%)microcomposite `

sPS/C10A (5-wt%)nanocomposite


240 260 280 300

T emp (oC)

Hea

t fl

ow (

End

o) (

offs

et)

(a)

(b)

(c)

(d)

Tmax = 290 oC, tm ax = 10 m in (a) s-PS (neat)(b) Na-MMT(5% )(c) C10A(5% )(d) C10A(10%)

P1P2

P3

P4

0 10 20 30

2(degree)

Inte

nsit

y (a

.u.)

Tmax = 290 oC, tm ax = 10 m in

(a)

(b)

(c)

(d)

(a) s-PS (neat)(b) Na-MMT(5% )(c) C10A(5% )(d) C10A(10%)

Polymorphism in sPS/clay nanocomposites Polymorphism in sPS/clay nanocomposites melt crystallized at 240melt crystallized at 240ooCC

tc = 30 min

DSCDSC XRDXRD


Characterization sPS/clay Nanocomposites Characterization sPS/clay Nanocomposites Melt crystallized at 235Melt crystallized at 235ooCC

240 260 280 300

T emp (oC)

Hea

t fl

ow (

End

o) (

offs

et)

(a)

(b)

(c)

Tmax = 290 oC, tm ax = 10 m in (a) s-PS (neat)(b) Na-MMT(5% )(c) C10A(5% )

P1

P2P3

P4

0 10 20 30

2(degree)

Inte

nsit

y (a

.u.)


(a)

(b)

(c)

(a) s-PS (neat)(b) Na-MMT(5% )(c) C10A(5% )

tc = 30 min

DSCDSC XRDXRD


Crystal forms in sPS/clay nanocomposites Crystal forms in sPS/clay nanocomposites melt crystallized at 245melt crystallized at 245ooCC

260 280 300

T emp (oC)

Hea

t fl

ow (

End

o) (

offs

et)

(a)

(b)

(c)


P1P2

P3

0 10 20 30

2(degree)

Inte

nsit

y (a

.u.)


(a)

(b)

(c)


tc = 60 min

DSCDSC XRDXRD


Melt crystallization behavior of Melt crystallization behavior of sPS/clay nanocomposites at 250sPS/clay nanocomposites at 250ooC C

250 260 270 280 290 300

T emp (oC)

Hea

t fl

ow (

End

o) (

offs

et)

(a)

(b)

(c)


P1 P2 / (=P2+P3)

0 10 20 30

2(degree)

Inte

nsit

y (a

.u.)


(a)

(b)

(c)


tc = 60 min

DSCDSC XRDXRD


800X 10μm 800X 10μm800X 10μm

sPS/Na-MMT(5-wt%)microcomposite

sPS/C10A (5-wt%)

nanocomposite

sPS (neat)

Effect of layered silicates in Effect of layered silicates in spherulitic dimension of sPSspherulitic dimension of sPS

All the samples were melt crystallized at 240C for 30 min (Tmax = 290C, tmax = 10 min)

Average maximum diameter of spherulites

~40 m ~25 m ~15 m


ConclusionsConclusionsThe sPS molecules were successfully intercalated into the organo-clay galleries. TEM analysis revealed a mixed morphology of an intercalated/exfoliated structure in the sPS/clay nanocomposites.

A significant alteration of the polymorphism in the sPS matrix was observed by the inclusion of different nano-layered clays. The temperature regime of the -crystal formation in sPS was found to expand considerably and the organo-clays favored the formation of -phase in addition to the -phase, even at high Tc of 250C.

Pristine clay (Na-MMT) was dispersed in the sPS matrix more coarsely with aggregated structures, behaved differently in its nucleating action and only larger spherulites of -form of sPS crystals were induced to grow at all the available Tc’s.

the clay dispersibility in the sPS matrix is assumed to play a pivotal role in altering the crystalline structures. The inclusion of the organo-clay with nano-scale dispersibility promoted the rapid formation of -forms, which developed spherulites of smaller dimension as compared the -forms. However, the proportion of -phase was decreased with higher loading (> 5-wt%) of organo-clay due to poor dispersion.

The peak 2 (P2) for melt-crystallized sPS in DSC analysis was further confirmed to correspond to the -phase, as it was almost absent in the sPS/Na-MMT composites.


Polymorphic Crystal Forms and Melting Behavior of PoPolymorphic Crystal Forms and Melting Behavior of Poly(butylene adipate)ly(butylene adipate)


IntroductionIntroduction

• Polymorphic structure of Poly(butylene adipate)(PBA) was reported by Minke and Blackwell in 1979. They have identified two types of polymorphic crystals exhibited in crystalline PBA samples. -from crystal was characterized as a monoclinic unit cell, and -form was packed as an orthorhombicunit cell.

• For PBA, in the previous paper, it was indicated that the formation of - and -form crystal was dependent on the melt crystallization temperatures.

• In this study, we attempted to explore the relationships between the polymorphic crystals and the multiple melting peaks.


ExperimentalExperimental

Material UsedMaterial UsedPoly(butylene adipate)(PBA) Poly(butylene adipate)(PBA) (Aldrich Chem. Co.)

Mw=12,200 and Mn=9,540 with a polydispersity of 1.28.

• Purification: PBA was reprecipitated from chloroform into cold methanol (ca. –10oC). And then, the sample was dried in the vacuum oven at 40oC for 7 days to remove the solvent.

n

(CH2)4 O C

O

(CH2)4 C

O

O


Complex Melting Peaks and Characterization of Complex Melting Peaks and Characterization of Crystal forms in PBACrystal forms in PBA

WAXD DSC

1 5 2 0 2 5 3 02d eg ree

Inte

nsi

ty(o

ffse

t)

2 5 oC

2 9 oC

2 9 .5 oC

3 0 oC

3 5 oC

T c=

3 0 4 0 5 0 6 0 7 0T em p era tu re(oC )

En

dot

her

mic

hea

t fl

ow (

offs

et s

cale

)2 8 oC

3 1 oC

3 0 .5 oC

3 0 oC

2 9 .5 oC

2 9 oC

2 8 .5 oC

P 1

P 1 P 3

P 3

P 2

P 2

P 4

P 4

T c=


PBA isothermally melt-crystallized at 29.5 PBA isothermally melt-crystallized at 29.5 ooC for vaC for various timesrious times

3 0 4 0 5 0 6 0 7 0T em p era tu re(oC )

En

dot

her

mic

hea

t fl

ow (

offs

et s

cale

)

0 .5

0 .7

6 0

3 0

2 0

1 0

1 .5

1 .0

P 1

P 1

P 1

P 1

P 3

P 3

P 3

P 3P 4

P 4

P 4

P 2 t c(m in )=


PBA (TPBA (Tcc= 29.5= 29.5ooC) and scanned at various ratesC) and scanned at various rates

(tc=30min)3 0 4 0 5 0 6 0 7 0

T em p era tu re(oC )

En

dot

her

mic

hea

t fl

ow (

offs

et s

cale

)

2 .5

5

1 0

2 0

P 1

P 1

P 1

P 2P 4

P 4

P 2 + P 3

P 2 + P 3 + P 4

S ca n ra te (oC /m in )

P 3


Dynamically cooled PBA at various rates (TDynamically cooled PBA at various rates (Tcc=29.5=29.5oo

C)C)DSC WAXD

2 0 4 0 6 0T em p era tu re(oC )

En

dot

her

mic

hea

t fl

ow (

offs

et s

cale

)

c oo lin g ra te= (O C /m in )

0 .5

1 .0

2 .5

10

20

40

P 1P 2 P 3

P 4

P 1

P 1

P 1

P 3

P 3

P 3

P 2

P 2

P 4

P 4

1 5 2 0 2 5 3 02d eg ree

Inte

nsi

ty(o

ffse

t)

1

1 0

2 0

co o lin g ra te= (oC /m in )


PBA sample melt-crystallized at 28PBA sample melt-crystallized at 28ooC was melC was mel

ted to 58ted to 58ooC and then quenched to 31C and then quenched to 31ooCC

3 0 4 0 5 0 6 0 7 0T em p era tu re(oC )

2 4

2 6

2 8

En

dot

her

mic

hea

t fl

ow(W

/g)

P 1P 3

1 5 2 0 2 5 3 0

2d eg ree

-1 0 0 0

0

1 0 0 0

2 0 0 0

3 0 0 0

Inte

nsi

ty(c

oun

ts)


PBA (TPBA (Tcc=31=31ooC) melted to different TC) melted to different Tmm and then and then

quenched to 28quenched to 28ooCC

3 0 4 0 5 0 6 0 7 0T em p era tu re(oC )

En

dot

her

mic

hea

t fl

ow (

Off

set

Sca

le)

P 1P 2

P 3

P 4

P 1

P 2

P 3

P 4

(3 )

(1 )

(2 )

T m = 6 5 oC

6 0 oC

5 5 oC

1 5 2 0 2 5 3 02d egree

Inte

nsi

ty(o

ffse

t) (1 )

(2 )

(3 )

T m = 6 5 oC

T m = 6 0 oC

T m = 5 5 oC


Comparison of the melting behaviors of Comparison of the melting behaviors of -for-form crystal melted to various temperaturesm crystal melted to various temperatures

4 0 5 0 6 0 7 0T em p era tu re(oC )

1 0

1 1

1 2

1 3

En

dot

her

mic

Hea

t f

low

(W/g

)

4 8 oC

5 0 oC


En

dot

her

mic

hea

t fl

ow(o

ffse

t sc

ale)

6 3 .7 J /g

H f = 5 6 .2 J /g

4 8 oC (2 h r)

5 0 oC (2 h r)

3 9 .6 J /g4 8 oC (0 .5 m in )

T a =


X-ray diffractograms for PBA (TX-ray diffractograms for PBA (Tcc=31=31ooC) melteC) melte

d and annealed to various temperaturesd and annealed to various temperatures

1 5 2 0 2 5 3 02d eg ree

Inte

nsi

ty(o

ffse

t)

5 0 oC

4 8 oC

T a =


Comparison of the melting behaviors of Comparison of the melting behaviors of -for-for

m crystal melted to various temperaturem crystal melted to various temperature

3 0 4 0 5 0 6 0 7 0T em p era tu re(oC )

En

dot

her

mic

hea

t fl

ow

5 1 oC

5 3 oC


En

dot

her

mic

hea

t fl

ow(o

ffse

t sc

ale)

6 5 .6 J /g

H f = 5 1 .3 J /g

5 3 oC (2 h r)

5 1 oC (2 h r)

4 7 .4 J /g 5 1 oC (t= 0 .5 m in )

T a =


X-ray diffractograms for PBA (TX-ray diffractograms for PBA (Tcc=28=28ooC) melteC) melte

d to various temperaturesd to various temperatures and annealedand annealed

1 5 2 0 2 5 3 02d eg ree

Inte

nsi

ty(o

ffse

t)

5 3 oC

5 1 oC

T a =


ConclusionConclusion

• The formation of -form crystal can be favored in the crystallization of PBA under these two conditions: (1) slow cooling from the molten state, (2) melt crystallization at high temperatures.

• The -form crystal can be formed under these two conditions: (1) melt crystallization at lower temperatures, (2) at fast cooling rates from the melt.

• The -form crystal which was heated to melt produced two endothermic peaks (P1 and P3). P2 and P4 appeared when -from crystal was melted. As - and -form crystals coexisted, the melting behaviors for the crystals showed four peaks (P1-P4) on the DSC trace.


Miscibility in Ternary Blends:

PVAc/PVPh/PMMA

Part 1


PVPh Mw = 22,000 g/mol Tg = 148.3oC

Polysciences, Inc.

PMMA Mw=100,000 g/mol (GPC) Tg = 87.1oC

Polysciences, Inc.

PVAc Mw = 260,000 g/mol (GPC) Tg = 35.4oC

Scientific Polymer Products, Inc.

THF b.p=66oCMEK b.p=79.6oC Cyclohexanone b.p=156.7oC

OH

C C( ) n

n)( CCH2

CH3

C O

O

3CHCH2 CH( )

OCOCH3

n

Materials

Experimental Part

Solvent


Experimental Part(Contd.)

Sample Preparation

The blend samples were prepared by solvent-casting (THF,MEK and cyclohexanone).When completely mixing that The blend samples were cast at 45oC for 24 hr. Samples were subjected to vacuum degassing at 80oC for one week

Apparatus

Optical light microscope (Nikon Optiphot-2, POL)Different scanning calorimeter (Perkin-Elmer DSC-7)Scanning electron microscope (SEM, JEOL JXA840)


Results and Discussion

POM for ternary PVAc/PVPh/PMMA phase diagram :

PVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

PMMA

0

10

20

30

40

50

60

70

80

90

100

PVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

PMMA

0

10

20

30

40

50

60

70

80

90

100

PVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

PMMA

0

10

20

30

40

50

60

70

80

90

100

THF cyclohexanone MEK


PVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

PMMA

0

10

20

30

40

50

60

70

80

90

100

POM for ternary PVAc/PVPh/PMMA MEK casting phase diagram :

Results and Discussion (Contd.)


PVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

PMMA

0

10

20

30

40

50

60

70

80

90

100

>300

>300

>300>300 >300

>300 >300

295 286 288

272259

>300

>300

Results and Discussion (Contd.)

LCST Behavior :


DSC thermograms for PVAc/PVPh/PMMA ternary blends heated at 20oC/min

0 4 0 8 0 1 2 0 1 6 0

T em p era tu re ( oC )

End

othe

rmic

hea

t flo

w (

offs

et s

cale

)

P V A c/P V P h /P M M A = x /y /z5 /7 0 /2 5

2 5 /7 0 /5

1 0 /6 0 /3 0

8 0 /1 0 /1 0

9 0 /5 /5

3 0 /6 0 /1 0

4 0 /5 0 /1 0

3 5 /5 0 /1 5

0 4 0 8 0 1 2 0 1 6 0

T e m p e ra tu re ( oC )

Eno

ther

mic

hea

t flo

w (

offs

et s

cale

)

P V A c/P V P h /P M M A = 1 /x /1

5 /9 0 /5

1 0 /8 0 /1 0

1 5 /7 0 /1 5

2 0 /6 0 /2 0

2 5 /5 0 /2 5

3 0 /4 0 /3 0

4 5 /1 0 /4 5

5 0 /0 /5 0

Results and Discussion(Contd.)


DSC traces of the physical-aged PVAc/PVPh/PMMA blends (ageas at 70oC for different time)

0 40 80 120 160


End

othe

rmic

hea

t flo

w (

offs

et s

cale

)

P V A c/P V P h /P M M A T a= 7 0 oC 2 4 h r

1 0 /6 0 /3 0

2 0 /6 0 /2 0

3 0 /6 0 /1 0

3 5 /5 0 /1 5

4 0 /5 0 /1 0

2 5 /5 0 /2 5

DSC traces of the physical-aged PVAc/PVPh/PMMA blends (ageas at 70oC for various composition)

0 4 0 8 0 1 2 0 1 6 0


End

othe

rmic

hea

t flo

w (

offs

et s

cale

)

P V A c/P V P h /P M M A = 2 0 /6 0 /2 0 T a= 7 0 oC

2 4 h r

1 6 h r

8 h r

0 h r




PVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

PMMA

0

10

20

30

40

50

60

70

80

90

100

91.3

117

113

102109 97

99.2 86.3

102 82.5 75.8 75

40

40

Tg value for ternary PVAc/PVPh/PMMA phase diagram :


THE observed Tg data by DSC vs the Tg Values calculate by Fox equation

giii

g TWT //1

This finding might imply that interactions among the components are weak.


0 4 0 8 0 1 2 0 1 6 0

T g ,c a l (oC )

0

4 0

8 0

1 2 0

1 6 0

Tg ,o

bs (o C

)

P V A c/P V P h /P M M AT ern a ry B len d S ystem

NCKU-PRLPolym. Res. Lab.Nation Cheng Kung Univ.SEM micrographs of PVAc/PVPh/PMMA ternary blends of virious compositions.

5/90/5

8000X

10/80/10

6000X

15/70/15

5000X

20/60/20

5000X

10/60/30

5000X

30/60/10

8000X

40/50/10

8000X

80/10/10

1800X

35/50/15

5000X

NCKU-PRLPolym. Res. Lab.Nation Cheng Kung Univ.SEM micrographs of PVAc/PVPh/PMMA ternary blends of virious compositions.

5/70/25

5000X

25/70/5

5000X

90/5/5

5000X


LPVAc/PVPh/LPMMA

Part 2


PVPh Mw = 22,000 g/mol Tg = 148.3oC

Polysciences, Inc.

LPMMA Mw=15,000 g/mol (GPC) Tg = 75.8oC

Aldrich Chemical Company, Inc.

LPVAc Mw = 12,800 g/mol (GPC) Tg = 31.3oC

Aldrich Chemical Company, Inc.

solvent

MEK b.p=79.6oC

OH

C C( ) n

n)( CCH2

CH3

C O

O

3CH

CH2 CH( )

OCOCH3

n

Materials

Experimental Part



LPVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

LPMMA

0

10

20

30

40

50

60

70

80

90

100

POM for ternary LPVAc/PVPh/LPMMA phase diagram :


DSC thermograms for LPVAc/PVPh/LPMMA ternary blends heated at 20oC/min

0 4 0 8 0 1 2 0 1 6 0


End

othe

rmic

hea

t flo

w (

offs

et s

cale

)

L P V A c/P V P h /L P M M A = 1 /x /1

1 0 /8 0 /1 0

1 5 /7 0 /1 5

2 0 /6 0 /2 0

2 5 /5 0 /2 5

3 0 /4 0 /3 0

4 5 /1 0 /4 5

5 0 /0 /5 0

5 /9 0 /5

3 5 /3 0 /3 54 0 /2 0 /4 0

0 4 0 8 0 1 2 0 1 6 0


End

othe

rmic

hea

t flo

w (

offs

et s

cale

)

L P V A c/P V P h /L P M M A = x /1 /1

0 /5 0 /5 0

2 0 /4 0 /4 0

4 0 /3 0 /3 0

6 0 /2 0 /2 0

8 0 /1 0 /1 0



0 4 0 8 0 1 2 0 1 6 0


End

othe

rmic

hea

t flo

w (

offs

et s

cale

)

L P V A c/P V P h /L P M M A = 1 /1 /x

1 0 /1 0 /8 0

2 0 /2 0 /6 0

3 0 /3 0 /4 0

4 0 /4 0 /2 0

5 0 /5 0 /0

0 4 0 8 0 1 2 0 1 6 0


End

othe

rmic

hea

t flo

w (

offs

et s

cale

)

L P V A c/P V P h /L P M M A = x /y /z

1 0 /5 0 /4 0

1 0 /3 0 /6 0

4 0 /5 0 /1 0

6 0 /3 0 /1 0

5 /7 0 /2 5

2 5 /7 0 /5




LPVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

LPMMA

0

10

20

30

40

50

60

70

80

90

100

109

101

89.2

81.3

70.8

116

97.9 59.165.893.7

60.872

59 57.5 53.7 46.6

36.2

35

71.6

59

80

105 87.5


Tg value for ternary LPVAc/PVPh/LPMMA phase diagram :


THE observed Tg data by DSC vs the Tg Values calculate by Fox equation

giii

g TWT //1

This finding might imply that interactions among the components are weak.


0 4 0 8 0 1 2 0 1 6 0

T g ,c a l (oC )

0

4 0

8 0

1 2 0

1 6 0

Tg,

obs

(o C)

P V A c/P V P h /P M M AT ern a ry B len d S y stem


60

80

100

120

140

0

1020

3040

5060

40

50

6070

8090

100

Tem

pera

ture

(T

g,on

set)

PVAc

PVPh


Effect of Mw on Tg values. （ HMW PVAc/PVPh/PMMA ）

（。 LMW LPVAc/PVPh/LPMMA ）


LPVAc/PVPh/LPMMA

Cyclohexanone solvent and co-precipitated

Part 3


Experimental Part

Sample Preparation

The blend samples were prepared by solvent-casting (cyclohexanone).When completely mixing that the blend samples were cast at 50oC and 90oC for 24 hr. Samples were subjected to vacuum degassing at 80oC for one week

Apparatus

Optical light microscope (Nikon Optiphot-2, POL)


POM for ternary LPVAc/PVPh/LPMMA cyclohexanone casting at 50oC sample ：

LPVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

LPMMA

0

10

20

30

40

50

60

70

80

90

100




POM for ternary LPVAc/PVPh/LPMMA cyclohexanone casting at 90oC sample ：

LPVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

LPMMA

0

10

20

30

40

50

60

70

80

90

100



LPVAc0 10 20 30 40 50 60 70 80 90 100

PVPh

0

10

20

30

40

50

60

70

80

90

100

LPMMA

0

10

20

30

40

50

60

70

80

90

100

0 4 0 8 0 1 2 0 1 6 0

T e m p e ra tu re ( oC )E

ndot

herm

ic h

eat f

low

(of

fset

sca

le )

L P V A c/P V P h /L P M M A c o -p re c ip ita ted

4 5 /1 0 /4 5

5 0 /0 /5 0


DSC for ternary LPVAc/PVPh/LPMMA phase diagram.


Conclusion

In this ternary blend of PVAc/PVPh/PMMA where PVPh is miscible with each of the other component, more than 50wt% PVPh was required to cause miscibility between PVAc and PMMA.

Phase boundary of LPVAc/PVPh/LPMMA ternary blend investigated by DSC shows that miscibility window was increased obviously. Furthermore, the Tg value of LPVAc/PVPh/LPMMA was less than PVAc/PVPh/PMMA system.

Blend prepared by cyclohexanone solvent casting and co-precipitated (MEK-hexane) were found to be immiscible.


Chiang Chih Pei


System

1. The blend of Poly(p-vinylphenol) (PVPh) /

Poly(1,6-hexamethylene adipate)(PHA)

2. The blend of Poly(p-vinylphenol) (PVPh) / Poly(ethylene azelate)(PEAz)

3. The blend of Poly(p-vinylphenol) (PVPh) / Poly(hexamethylene sebacate)(PHS)


2. Poly(1,6-hexamethylene adipate)(PHA)

Tm:55~65°C Mn: 3,800 (by GPC Mw: 13000) Aldrich Inc.

CH 2 O 2CHO C C

O O

n6 4

1. Poly(p-vinylphenol) (PVPh)

Tg:148°C Mw:22,000 Polysciences Inc.

CH 2 CH

OH

n

Part.1 The blend of PVPh/PHA


Methods

Sample preparation

All polymers blends via solution-casting. Solutions were prepared in tetrahydrofuran (THF) at a concentration of 4 g polymer/ 100 mL solvent to obtain clear solution mixtures at room temperature; then mixtures were cast at 45°C onto hot stage for 24hr. The solution-cast films were dried for a week in 40°C vacuum oven.

Apparatus

Polarizing optical microscope, POM

Differential scanning calorimeter, DSC


DSC traces of the PVPh/PHA blends

-40 0 40 80 120 160 200

T em p e ra tu re ( oC )

End

othe

rmic

hea

t flo

w (

offs

et s

cale

)

1 0 0 /0

9 0 /1 0

7 0 /3 0

5 0 /5 0

3 0 /7 0

P V P h /P H A(2nd run)


PVPh/PHA=0/100 PVPh/PHA=10/90

PVPh/PHA=30/70

POM graphs of PVPh/PHA blends after melt-crystallized at 30oC



PVPh/PHA=30/70




PVPh/PHA=30/70




PVPh/PHA=30/70



Part.2 The blend of PVPh/PEAz

2. Poly(ethylene azelate)(PEAz)

Tg:-50 °C Tm:55°C Mw:50,000 SP2 Inc.

1. Poly(p-vinylphenol) (PVPh)

Tg:148°C Mw:22,000 Polysciences Inc.

CH 2 CH

OH

n


Methods

Sample preparation

All polymers blends via solution-casting. Solutions were prepared in tetrahydrofuran (THF) at a concentration of 4 g polymer/ 100 mL solvent to obtain clear solution mixtures at room temperature; then mixtures were cast at 45°C onto hot stage for 24hr. The solution-cast films were dried for a week in 40°C vacuum oven.

Apparatus

Polarizing optical microscope, POM

Differential scanning calorimeter, DSC


Thermodynamic reversibility

-2oC/min

PVPh/PEAz=90/10

-2oC/min

PVPh/PEAz=80/20

-2oC/min

PVPh/PEAz=70/30

heat to above UCST cool to r.t.


Check the UCST behavior

+2oC/min +2oC/min

(B) after melt-blending and casting

(A) by melt-blending

as -cast transiting heat to above UCST

Using melt-blending to prepare PVPh/PEAz=70/30 binary blend sample, then dissolving in THF (4wt%); and casting at 45°C onto hot stage for 24hr. The solution-cast films were dried for 3days in 40°C vacuum oven.


Clarity point of the PVPh/PEAz blends

one phase

one phase

phase separation

UCST

0 2 0 4 0 60 80 100

P V P h w t(% ) in b in a ry m ix tu res

0

40

80

120

160

200C

lari

ty p

oin

t (o C

)


DSC traces of the PVPh/PEAz blends casting at 45oC

-6 0 0 6 0 1 2 0 1 8 0

T em p era tu re(oC )

En

doth

erm

ic h

eat

flow

(of

fset

sca

le)

100 /0

90 /10

80 /20

70 /30

60 /40

50 /50

40 /60

30 /70

P V P h /P E A z (a s ca st)


DSC traces of the PVPh/PEAz blends after quenching from 200oC

-6 0 0 6 0 1 2 0 1 8 0

T em p era tu re (oC )

En

dot

herm

ic h

eat

flow

(of

fset

sca

le)

1 0 0 /0

9 0 /1 0

8 0 /2 0

7 0 /3 0

6 0 /4 0

5 0 /5 0

4 0 /6 0

3 0 /7 0

P V P h /P E A z (2 n d ru n )


Clarity point temperature and Tg in PVPh/PEAz binary blends

PVPh/PEAz Clarity point(oC) 1st Tg(oC) 2nd Tg(oC)

0/100 x -56.3 -58.3

10/90 x -55.3 -56.5

20/80 x -46.3 -46.3

30/70 x -35.8 -34.7

40/60 x -17.6 -11.6

50/50 x -5.2 10.3

60/40 144 8.5 , 98 37.2

70/30 162 12.5 , 96.5 46

80/20 167 27.5 , 101.5 69.2

90/10 176 53.5 , 102 95.6

Documents

NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 奈米化工與高分子材料 2003/11/8 報告人 : 吳逸謨