Synthesis and Characterization of Poly(N-isopropylacrylamide) Containing Polydimethylsiloxane    Polydimethylsiloxane poly(N-isopropylacrylamide)
 

Printed in the Republic of Korea

Polydimethylsiloxane
 poly(N-isopropylacrylamide)

  

 *

  

(2001. 2. 1 )

Synthesis and Characterization of Poly(N-isopropylacrylamide) Containing Polydimethylsiloxane

Young-Sung Kim, Min-Ae Bae, and Koo-Sik Yoon*

School of Chemistry and Biological Sciences, University of Ulsan, Ulsan 680-749, Korea (Received February 1, 2001)

.   methacryl  polydimethylsiloxane(PDMS)   poly(N- isopropylacrylamide)(PNIPAAm)  PDMS  PNIPAAm !". IR, DSC #$

%&'( ) *+,-. DSC *+ / PNIPAAm PDMS0 11 234 5- 670 &#

89:!-., PNIPAAm( T^g0 PDMS( ;# <= >?@ AB,". C DE FG HIE

*+ / PDMS( ;# <= HIE0 AB,-J lower critical solution temperature(LCST)0 K L  M!". HI4 NO( DSC PQ/E LCST0 PDMS( ; RS TU V0 & 8 9,".

ABSTRACT. Poly(N-isopropylacrylamide) (PNIPAAm) containing polydimethylsiloxane (PDMS) was synthesized using PDMS as crosslinking agent, and characterized by IR and DSC. It seems that the copolymer has separated phases, PNIPAAm and PDMS. The Tg of PNIPAAm was decreased in accordance with the increase of PDMS-contents. The swelling behavior of polymer in water was examined with the function of temperature and PDMS-contents as well. The equilibrium swelling ratio of polymer in water was decreased with increasing PDMS-contents, but lower critical solution temperature (LCST) was not significantly affected by the incorporated PDMS-contents.

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 Ša9 ‹E AB". DE  Au0 RS ŒU VY Ša ) Ž0 ^ 

:„ ". Mukae ‘Z IPN NO  %&

( DE  Au *+,Y,^11-12 Minghong ‘Z N-isopropylacrylamide(NIPAAm) polypropylene %

‡’“f” %&( >`de r •Y,-.,¹³

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O  DE( XA *+,".¹⁵™

Lowe ‘Z šln‰  ;O_ NIPAAm – N %&( ›; œ Ša )  Y

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 3a ¡¢ UY 0 £¤ B9 polydimethylsiloxane(PDMS)  #$

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¥a ) œ DE Au *+,".

  . Octamethylcyclotetrasiloxane(OMTS)

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–¬(Œ)( EP¦

lithium aluminium hydride(LiAlH4) ­Y ®¯f”

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 hexaney 7/Q +$,". f9 N,N- azobisisobutyronitrile(AIBN)Z Junsei Chemical+( GR¦

 7/Q +$,-., tolueneZ Junsei Chemical +( EP¦ Q M# +$,". Methacryloyl chloride 0 methacrylate acid_ thionyl chloride² 

+$,". HexaneZ Katyama>« –¬(Œ)( EP¦

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 a[Ž 2´´EŠ(FT-IR)0 Unicam+(

Mattson 5000, Differential Scanning Calorimetry (DSC)0 Thermal Analysis+( 2910 +$,".

α αα

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 . 100 mL µ¶ ·¸ š‡g¹ OMTS_ 2

; *º9 BATS Table 1 Jb»  q# 11

­Y  §£9 TMAH 0.30 mL 11 ­„ A¼

 ± )B ½¤0 v¾- ¿ À – Á®

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oxane( 2;Z ( amine aQ0 v¾-

 ^,".  NO( 2; Table 1 J bc!".

a,
-Bis(3-methacrylamidopropyl)polydimethylsiloxane (MPDMS) . 100 mLµ¶ ·¸ š‡g¹ Ü

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( ßà  "‚, septa rubber á^ âY –

 )B Á®,". š‡g¹ ゠Näy  ÃÄ Å-=y APDMS Þ( ßà( methacryloyl chloride  v
@ å„æç". " ­Z ± Šè

4f? Ì tu fÈ-. pyridinium salt   ÑY $Ú   ©Û³- °* ± A¼ 

$£_ Îtu`( methacryloyl chloride_ pyridine

Ñ,".

PNIPAAm  PDMS  PNIPAAm .

PNIPAAmZ 100 mL µ¶ ·¸ š‡g¹ 0.0884 mol (10.0 g)( NIPAAm 9 ethylene glycol dime- thacrylate 0.333 mL, f9 AIBN 0.290 g ­Y DMF 10.6 mL(10.0 g) Ý9 ± )B – Á®

 € é ± 1.5 mm( Y ê ?ë ì 10×

10 cm²3í +# Œ+ Œá 24f? ÆÇ

65^oCy N,".  ± NO è( DMF  Ñ Ë ` è î%„ ßY ¿À <¯

ïðŒ!". ™ MPDMS   NIPAAm(

NZ "‚ q# ,". 100 mLµ¶ ·¸ š

‡g¹MPDMS_ NIPAAm, AIBN, toluene Table 2 Jb»  q# 11 ­Z ± –, )B Œá Table 1. The feed of monomer and average molecular weight of PDMS synthesized

APDMS Feed (g) Mn (g/mol)

OMTS BATS Calcd Found

S-1 17.9720 2.9821 1730 1770

S-2 18.9837 3.9562 1440 1470

S-3 16.0175 4.4732 1180 1200

0 v¾- B Ñ "‚  ÃÄ ńy

€ ñ!". #& òó 1.5 mm( Y ê ô õö

3í +# Œá 60^oCy 24f? ÆÇ N

,".  NO' ¨©ª 48f? ÆÇ î%

„ NO è ÷:„ 0 ølù Îtu`  Ñ,". "f <¯ ¿ À î%„ NO è(

¨©ª údû Ñ ± HI4 5˜y 5×5 mm²

¹ G Ô <¯ •ü,".  NO(

^* Scheme 1 Jbc!".

  . 1 NO ýÅ 100^oC  U4 – nþy l ÆÇ ÿ2û °*f
±   Ä PQY, <¯ è î%„ 11( DEy Ì #5  Ä( L  M Ö×U vÁ Ô  Ä

PQ,". #Ö f 11 4@ PQ 

 +$,". HIE(degree of swelling) Š0 ÒZ "‚ q".

(%) =

  

 .  NO( a[Ž g“‡ N Polymer AŠ¥( & Fig. 1 Jbc!". 1680~

1630 cm⁻¹y0 NIPAAm( amide( C=O \…Æ

, 1000~1100 cm⁻¹0 PDMS( Si-O-Si( › 

 11 JbJ 0 &   ". #&- –N

O(  89  !". C PDMS( ;

# <  NIPAAm( C=O( › 0 ABY Si-O-Si( › 0 < |  !". Fig. 1(

A-4, A-5( 2300 cm⁻¹ JbJ0 ›0 CO²( &

- Š( 5˜ F‡ JbJ0 &#". Polymer B _ CE  / Jbc!". C  NO N PDMS( ;# Z °* –NO( ó¤ ©

 >?(  Jbc!0 #¿ )Z 3 d# DE(T^g) # ðŒ Z PDMS :„ 

Ö#‡Y 14". C ` HI4 NO( ó¤

0 PNIPAAm# € g¿U0  Ê PDMS( ;

# <  Ša ‹E <,". %¿

PDMS PNIPAAm Eá- PNIPAAm   ( 9 Ša ‹E ƒ  "0 & | 

!".

  . Fig. 2 NO'( DSC /

  -  

 
100

  

Table 2. The feed of MPDMS, NIPAAm and AIBN

Polymer Feed (g)

MPDMS NIPAAm AIBN Toluene

A-1 A-2 A-3 A-4 A-5 B-1 B-2 B-3 B-4 B-5 C-1 C-2 C-3 C-4

0.4068(S-1) 0.8015(S-1) 1.2066(S-1) 1.6033(S-1) 2.0053(S-1) 0.4097(S-2) 0.8062(S-2) 1.2030(S-2) 1.6016(S-2) 2.0060(S-2) 0.4031(S-3) 0.8043(S-3) 1.2038(S-3) 2.0048(S-3)

3.6039 3.2044 2.8034 2.4050 2.0061 3.6001 3.2038 2.8055 2.4006 2.0079 3.6032 3.2046 2.8023 2.0044

0.0409 0.0408 0.0424 0.0413 0.0406 0.0419 0.0400 0.0416 0.0409 0.0415 0.0413 0.0413 0.0407 0.0401

4.05 4.07 4.01 4.00 4.02 4.02 4.06 4.03 4.01 4.01 4.02 4.08 4.03 4.04

*A, B and C stand for polymer containing S-1, S-2 and S-3, respectively.

Scheme 1.

Jbc!-. Table 30 °*4 NO'( 3 d

# DE(Tg) ' Jbc!". Tg( K L  M0

&- •ð PDMS_ PNIPAAm# 523 :„ "

Y •U., PDMS( ;# <  3 d#

DE ðU0 óS Jbc!". #¿ /0 PDMS  +$, Ö 523 ƒ„

„E U ¶y0 PDMS +( ƒ2#

 &-   -., rû PDMS( #  i Z NO C( ó¤ % AB Ì K %&Z PDMS( +#  E < Ö#

‡Y 14".

 . Fig. 3~50 11( DE FG N

O'( `  HIE(degree of swelling) Jbc

!". PDMS 4 PNIPAAm –NOE PNIPAAm ( d—a9 DE XA •ŒY ". %¿J PDMS( ;#  HIE0  AB,0

#&Z ` ( HI# PNIPAAm( Ryõ ƒ

„J Ö PDMS( ;# <  % R#

AB Ö#‡Y 14". LCST0 32^oC ¶-

 # /0 "G Á_ ƒÁ,".¹⁰ C PDMS Fig. 1. IR spectra of Polymer A.

Fig. 2. DSC thermograms of PNIPAAm, Polymer A and sil- icone. (10^oC/min under N2).

Table 3. Glass transition temperature of the polymers (10^oC/min under N2)

Polymer Tg (^oC) Polymer Tg (^oC) Polymer Tg (^oC)

A-1 A-2 A-3 A-4 A-5

132.22 129.46 132.49 127.64 123.95

B-1 B-2 B-3 B-4 B-5

137.70 135.48 127.58 123.04 122.51

C-1 C-2 C-3 C-4 PNIPAAm

137.33 135.93 128.44 119.92 137.28 Fig. 3. The relationship between degree of swelling and tem- perature of Polymer A in pure water.

( ; FG LCST E K L  M!0 #&

Z PNIPAAm PDMS "G 5- 67 HI Z PNIPAAm5yõ ƒ„J Ö PDMS( RS

 TU V0 &- 14". Fig. 60 PDMS( 2

; FG HIE  Ë  PDMS

; Y 0 NO'( HIE Jbc!". % / 2; FG HIE0 K RS ŒU V0"0

& |  0 #&E PNIPAAm Rõ# `

HI"0 & "f 89 Œ!". %!Uõ PDMS( # Z Polymer C( ó¤ "G NO

•" HIE Z & |  0 #&Z E

  Ö HIE AB"Y 14". HIE v¾- ^ LCST DSC 89 Ë HI 4 NO DSC #$ ¥a ) *+,".

% / Fig. 7 Table 4 Jbc!". <¯ H

I4 NO 30^oC_ 40^oC +#y ›¥ peak J b0 #&Z DE ª‡A F‡ NO N(

NIPAAm Ë_ `2 — B/# "#:

„ ¥ ›0 /‡Y   ". DSC /y Fig. 4. The relationship between degree of swelling and tem-

perature of Polymer B in pure water.

Fig. 5. The relationship between degree of swelling and tem- perature of Polymer C in pure water.

Fig. 6. The relationship between degree of swelling and tem- perature of A-1, B-1 and C-1 in pure water.

Fig. 7. DSC thermograms of swelled polymer in pure water.

(10^oC/min under N2).

Table 4. LCST of the polymer by DSC (5^oC/min, under N2) Polymer LCST (^oC) Polymer LCST (^oC) PNIPAAm

B-1 B-2 B-3

31.94 32.48 31.73 32.64

B-4 B-5 A-1 C-1

30.51 31.82 32.22 31.93

E LCST HIE PQy_ q# 32^oC ¶ Jb J0 & 89  !0 PDMS( ; œ %&

( # Êy0 Ñ( RS TU V0 & • Œ

!". #¿ /0 `# :„ 0 PNIPAAmR

yõ HI# ƒ„†"0 & À Ì 89Ä :!".

 ð¹$%#“  polydimethylsil- oxane(PDMS)  ± #&  +$

N-isopropylacrylamide N- PDMS 

 poly(N-isopropylacrylamide)(PNIPAAm) !".

# –NO DSC ¥a r *+ / –N

O0 2( 5- 23:„ !-. PDMS( 

;# <  T^gZ >?@ AB,". C `

HI4 –NO0 DE XA DE ª‡=

`( ›;Z AB,-., PDMS( ;# <

= `( ›;Z AB,-J PDMS ;Z LCST

 RS ŒU V&". C HI4 NO DSC

 PQE LCST( L  M!".  ( Š

a ) Qa- *+ / PNIPAAm PDMS

 –Nf'= Ša )# (ð) 89  

!".

   

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