1.
서 론1)
.
. 1980
Corresponding author: e-mail: [email protected]
[1-6].
PU
ionomer N-methyl diethanol amine (MDEA) [7-10].
MDEA ionomer PU
PU
(hard segment) .
PU (micelle)
PU
김동민 ․ 방문수 ․ 김형중†
공주대학교 공과대학 신소재공학부
년 월 일 접수 년 월 일 채택
(2006 1 6 , 2006 1 25 )
Preparation and Properties of Water-borne PU Having Ionic Center onto Flexible Side Chain
Dong-Min Kim, Moon-Soo Bang, and Hyung-Joong Kim Department of Advanced Material Engineering, College of Engineering,
Kongju National University, Chungnam, 314-701, Kongju, Korea (Received January 6, 2006; Accepted January 25, 2006)
: isocyanate IP-75 hydroxyl
amino alcohol ionomer ionic center
polyurethane (PU) . NCO/OH , ionomer
PU , , , , , Tg, .
PU ionic center PU
.
Abstract: Three isocyanate groups of IP-75 and one hydroxyl group of various amino alcohols were applied for preparing cationic type water-borne polyurthane (PU) having ionic center onto flexible side chains. Average particle size, dispersion stability, viscosity, contact angle, surface energy, glass transition temperature (Tg), and adhesion strength of prepared water-borne PUs were measured and analyzed with different NCO/OH mol ratios, ionomers, and neutralizing agents. It was characterized that the prepared PU has a smaller particle size and a better dispersion stability than the conventional cationic water-borne PU containing ionic centers onto main chains.
Keywords:cationic, water-borne, polyurethane, ionic center, side chain
. PU
. 3 IP-
75 amino alcohol ionomer
PU .
PU NCO/OH , amino alcohol , ,
, , , , ,
(Tg) .
2.
실 험2.1. 재 료
Table 1 .
Aekyung IP-75 3 (-N=C=O)
PU ethyl acetate solid content 77 wt%
. Amino alcohol Aldrich dimethylethanolamine (DMEA) 3-dimethyl amino-1- propanol (DMAP) TCI 2-(2-diethylamino ethoxy)
ethanol (DEEA) .
Aldrich TERATHANE 1000 polyether glycol
(PTMG1000) 60oC
12 degassing
. Daejung chem-
ical 1,4-butanediol (1,4-BD) Junsei ethylene diamine (EDA), Aldrich isophorone diamine (IPDA)
. Yakuri chemical acetic acid (AA) Deajung hydrochloric acid
(HCl) formic acid (FA) . NCO
Acros organics 4-di- methyl amino pyridine, J.T.Baker acetic anhydride, Yakuri chemicals di-n-butyl amine, Deajung chem- ical hydrochloric acid, Alpha chemical bromo- phenol blue, Deajung chemical toluene
.
2.2. 양이온성 수분산 PU의 제조 Figure 1 IP-75 DMEA
PU . PU
. Me- chanical stirrer condenser, N2 gas
4-neck resin kettle 25oC IP-75 amino alcohol
PU PU
Figure 1. Reaction scheme of cationic water-borne PU.
NCO NCO%
PTMG1000 .
40oC NCO
FT-IR NCO
. NCO%
FT-IR NCO
. NCO
(neutralizing agent) 3 stirrer
deionized water dropping funnel FT-IR NCO
NCO .
Figure 1( ) . Table 2
PU
Reagent
name Molecular structure Company
Molecular weight (g/mol)
IP-75 Aekyung 801.05
DMEA Aldrich 89.14
DMAP Aldrich 103.17
DEEA TCI 161.24
IPDA Aldrich 170.3
. IP-75 :amino alcohol
1:0.88 . IP-75 trimethylol propane (TMP) IPDI 1:3
. IP-75 IPDI
NCO%
IP-75 . IP-75
801.05 g/mol IP-75 NCO
NCO% 14.89% 2.88 .
IP-75 IP-75 :
IPDI 0.88:0.12 0.96:
Table 2. Naming of Synthesized Water-borne PU Sample name IP-75 : amino alcohol
(mol ratio)
NCO/OH
mol ratio Applied amino alcohol Chain extender Neutralizing agent IPU-1
IPU-2 IPU-3 IPU-4 IPU-5 IPU-6 IPU-7 IPU-8 IPU-9 IPU-10
1 : 0.88 1 : 0.88 1 : 0.88 1 : 0.88 1 : 0.88 1 : 0.88 1 : 0.88 1 : 0.88 1 : 0.88 1 : 0.88
1.07 1.07 1.07 2 1.14 1 2 2 2 2
DMEA DMAP DEEA DMEA DMEA DMEA DMEA DMEA DMEA DMEA
1,4-BD 1,4-BD 1,4-BD 1,4-BD 1,4-BD 1,4-BD EDA IPDA 1,4-BD 1,4-BD
AA AA AA AA AA AA AA AA HCl FA
der) . amino
alcohol solid content
25% IP-75 : 1:
0.75 .
2.3. 양이온성 수분산 PU의 분석
2.3.1. (-NCO)
PU
FT-IR .
KRS-5 disc 60oC
. FT-IR Spectrum 1000 (Perkin Elmer) resolution 2 cm-1 6 scan 2263 cm-1
NCO .
PU
ASTM
D2572-97 NCO .
2.3.2.
Photal PAR- (Otsuka electronics) Dynamic Light Scattering (DLS) method
. Basic condition clock rate 8 (µsec), corre.channel 1024 (channel), accum times 200 pin- hole selector 0.1 . Cell
PU
cell chamber 3
(25oC) .
2.3.3.
DV- + Blookfield viscometer 3
25oC .
2.3.4. (Dispersion Stability) PU (haziness) (color)
. PU
culture tube 60oC 24
.
2.3.5. (Contact Angle) (Surface En- ergy)
PU 100oC PU
deionized water SEO
CT-A400 .
2.3.6. Glass Transition Temperature (Tg)
PU 70oC
differential scanning calorymetry
(DSC) Tg . -40
100oC, 10oC/min
. DSC DSC 2010 (TA instruments) .
2.3.7.
(buffing) 20 × 100 × 4 mm3 SBR
P-65 (Sang-shin) . PU
(polyaziridine) 1 wt%
SBR
100oC SBR
.
100oC 5 H25KS-0143
(H.T.E. England) 180°
.
결과 및 토론
3.
3.1. 수분산 PU의 합성
Figure 2 PU NCO
FT-IR . Figure 2
2263cm-1 NCO
IP-75 DMEA, PTMG1000
. NCO
. NCO
Figure 2. FT-IR spectra for each reaction step.
PU .
AA 1,4-BD
.
. polarizability,
ion pairing
[11]. AA FA HCl
rod climbing . FA HCl
H2O H2O
biuret linkage .
EDA IDPA
. 1 IP-75
.
PU Figure
1 . IPU-4
PU .
Figure 1 PU
. Figure 1 IPU-4
. H2O
1,4-BD .
Figure 1
EDA, IPDA .
Figure 3. Particle sizes of prepared water-borne PU with different amino alcohols and NCO/OH mol ratios.
3.2. 입 도
.
. Figure 3 amino alcohol NCO/OH
PU .
DMEA, DMAP, DEEA
. IP-75 amino
alcohol
.
PU PU
. Figure 3 amino alcohol DMEA, DMAP, DEEA
. PU
.
, ,
. NCO/OH
Figure 3 .
3.3. 점 도
Figure 4 amino alcohol NCO/OH
PU .
. , ,
.
(1) (effec-
Figure 4. Viscosities of prepared water-borne PU with dif- ferent amino alcohols and NCO/OH mol ratios
tive volume fraction of dispersed phase) [7].
(1)
,
, k .
( ) .
(electroviscous effect)
electroviscous effect
[7]. Figure 4 amino
alcohol DMEA, DMAP, DEEA
NCO/OH
. Figure 3
.
3.4. 분산안정성
Table 3 PU ,
. 60oC
(days) 30
* .
PU (transparent) 1.
(translucent) 2. (opaque) 3
. Amino alcohol DMEA, DMAP, DEEA ionomer
. PU
ionomer
Table 3. Dispersion Stability of Prepared Water-borne PU Sample name Dispersion stability
(days) Haziness Color IPU-1
IPU-2 IPU-3 IPU-4 IPU-5 IPU-6
20
*
*
*
* 14
3 1 1 2 3 3
White Yellow Yellow White White White
Figure 5. Schematic drawing of dispersion particles with different location of cationic centers.
PU electric double layer
(coalescence) .
PU ionomer
.
. Figure 1 ionomer
. PU
electric double layer . Figure 5
PU .
PU PU
.
3.5. 접촉각 및 표면에너지
Figure 6 PU
.
(wetting)
Figure 6. Contact angles and surface energies of prepared water-borne PU with different amino alcohols and NCO/OH mol ratios.
Figure 7. Adhesion strengths of prepared water-borne PU with different NCO/OH mol ratios.
.
.
. DMEA, DMAP, DEEA
PU
NCO/OH 1 ionomer
.
3.6. 접착강도
Figure 7 PU NCO/OH
. NCO/OH prepolymer
. PU NCO/OH
1 prepolymer
. PU
NCO/OH
. Figure 7 NCO/OH
. NCO/
Figure 8. DSC thermograms of prepared water-borne PU with different NCO/OH mol ratios.
OH
.
3.7. Glass Transition Temperature (Tg)
Figure 8 NCO/OH
PU DSC thermogram . PTMG1000 Tg
PTMG1000 Tm
. NCO/OH 1 Tg
. PU
Tg -50 20oC
PU 30.6 60.1oC Tg
. PU
(linear) PU
Tg
.
4.
결 론IP-75 amino alcohol
PU . 1,4-
BD AA
PU .
PU amino alco-
hol DMEA, DMAP, DEEA
.
PU PU
,
electric double layer
. Amino alcohol DMEA, DMAP,
DEEA .
. PU NCO/
OH 1 ,
. NCO/OH
1 ionomer
electric double layer
. NCO/OH 2 1
Tg
.
참 고 문 헌
1. U.S. Patent 4,198,330 (1980).
2. U.S. Patent 4,501,852 (1985).
3. U.S. Patent 4,705,840 (1985).
4. R. E. Tripak, Water-borne and Gigher Soids Coatings Symposium (1990).
5. R. D. Cody, Water-borne and Gigher Soids Coatings Symposium (1990).
6. Y. M. Lee, B. K. Kim, Y. J. Shin, and H. H. Cho, Polymer (Korea), 16, 547 (1992).
7. K. B. Choi, 6 , 0,
83 (1999).
8. D. W. Park, Y. K. Lee, and S. C. Kim, Polymer (Korea), 6, 2 (1982).
9. S. W. Lee, B. K. Oh, Y. M. Lee, S. T. Noh, and K. Y. Kim, J. of Ind. & Eng. Chem., 1, 1 (1990).
10. J. S. Lee and B. K. Kim, J. of Korean Fiber Soc., 30, 10 (1993).
11. H. Kim, J. of Ind. & Eng. Chem., 0, 0 (1994).
