Beruflich Dokumente
Kultur Dokumente
2013
Department of Organic Technology, Kaunas University of Technology, Radviln pl. 19, LT-50254 Kaunas, Lithuania
Department of Wood Technology, Kaunas University of Technology, Student St. 56, LT-514241 Kaunas, Lithuania
http://dx.doi.org/10.5755/j01.ms.19.1.3823
Received 14 September 2011; accepted 15 February 2012
Successful vinyl acetate radical emulsion polymerization in water with different type of industrial grade poly(vinyl
alcohol) were produced by semi continuous way. The poly(vinyl alcohol) type has crucial impact on dispersion
rheological as well on films and bonding strength properties. It should be stated that the films containing modified poly
(vinyl alcohol) has better water resistance and mechanical properties. Poly(vinyl alcohol) with higher ethylene moieties
content and high hydrolization degree determines extremely low viscosity of final dispersion.
Keywords: poly(vinyl acetate) dispersion, poly(vinyl alcohol), semi-continuous polymerization, rheological behavior,
wood bonding.
1. INTRODUCTION
equipped with reflux condenser, plastic stirrer, two separate feed streams, on-line thermometer. Successful semicontinuous VA emulsion polymerization was done with
radical initiation system hydrogen peroxide-tartaric acid.
At the beginning water solution of PVA, sodium acetate,
and tartaric acid (TA) was loaded into the reactor. Stirring
rate 170 rpm, temperature was maintained at 60 C.
Immediately after temperature was reached, under nitrogen
atmosphere, 10 wt.% of VAc and 50 wt.% of hydrogen
peroxide (HPO) of total amount was loaded. After
induction period (approx. 5 min. 10 min.) the temperature
increased up to 75 C 80 C and was kept until all HPO
and VAc were loaded continuously. Continuous monomer
loading and first load of TA was done ~15 min. after
beginning of polymerization. Formulations of prepared
dispersions are given in Table 2. After VAc and HPO were
loaded, second load of TA was done. Then reaction
temperature was increased up to 80 C 85 C, for final
monomer conversion. After dispersion production 15 wt.%
sodium hydroxide solution in water was used for pH
corrections up to 5. Before mechanical analysis of polymer
film all dispersions were plasticized with plasticizer
amount of 10 wt.% from dry matter of dispersion.
2. EXPERIMENTAL
2.1. Materials
Commercial
name of PVA
Viscosity,
mPas
Degree of
hydrolysis,
mol%
Degree of
polymerization/
molar mass
(g/mol)
Mowiol20-98
18.521.5
98.098.8
2800/125000
RS 1717
23.030.0
92.094.0
1700/80000
RS 2117
23.030.0
97.599.0
1700/75000
HR 30101
11.015.0
99.099.6
1000/45000
20.030.0
98.099.0
1700/80000
R 1130
38
Total,
g
10
90
380
50
50
43.8
Vinyl acetate
Hydrogen peroxide
1% solution in water
Tartaric acid, 20%
solution in water
Sodium acetate
PVA:
A. Mowiol 20-98
B. RS1717
C. RS2117
D. HR3010
E. R1130
Demineralized water
72
100
151st. load
132nd load
4.53
0.285
28.5
100
365
Dry matter, %
50
40
0.8
30
0.6
20
0.4
10
0.2
VAc, %
Compound
Initial charge,
wt. %
0
A
Dispersions
Dry matter, %
VAc, %
Viscosity, Pas
A
B
C
D
E
5 10 15 20 25 30 35 40 45 50
Shear rate, 1/s
210
180
153.1
150
120
90
60
30
5.0
0
A
0.7
4.1
Dispersions
PVA
type
Degree of
hydrolysis,
mol%
Dw ,
Dn ,
A
B
C
D
E
98.098.8
92.094.0
97.599.0
99.099.6
98.099.0
0.93
0.39
0.43
0.94
2.60
0.59
0.10
0.15
0.91
0.81
Dw / Dn
1.59
3.77
2.99
1.08
3.19
1.2
Flow Index
1
0.8
0.6
0.4
0.2
0
A
Dispersions
40
Sample
Fmax, kN/m
B, MPa
R, %
A
B
C
D
E
1.8
1.5
1.8
2.2
1.8
18.0
13.0
17.7
15.8
12.3
212
257
244
223
177
35
30
25
20
15
10
5
0
0
8 10 12 14 16 18 20 22
Time, days
Number of oscillations
A
B
C
D
E
55
57
56
47
67
345
353
345
341
348
20.0
18.0
16.0
14.0
12.0
10.0
8.0
6.0
18.1
16.6
17.6
75
66
14.5
12.2
51
43
28
100
90
80
70
60
50
40
30
Wood failure, %
Water adsorption, %
40
20
10
0
4.0
2.0
0.0
A
Dispersions
Bonding strenght, N/mm
Wood failure, %
41
1.2
1.1
1.1
1.0
0.8
0.5
0.6
0.4
0.2
0.0
0.0
0.0
REFERENCES
Dispersions
1.
4. CONCLUSIONS
Stable dispersions with various type and hydrolization
degree PVA were produced via semi-continuous radical
emulsion VAc polymerization. Influence of PVA on final
dispersion characteristics was investigated accordingly. It
was stated that ethylene modified PVA hydrolization
degree has similar influence on dispersion viscosity
properties as unmodified PVA i. e. higher hydrolization
degree of PVA determine lower viscosity and close to
dilatant behavior of final dispersion. Usage of super
hydrolyzed ethylene modified PVA determine extremely
low dispersion viscosity and dilatant behavior. Dispersion
produced with fully hydrolyzed silane modified PVA had
rheological properties rather similar to partially hydrolyzed
PVA. Particle size of dispersions was highly dependent on
PVA hydrolization degree as well to its chemical structure
and molecular weight. The ethylene moieties in PVA
determined formation of larger and more even particles.
Physicochemical properties of the plasticized films
produced with different type of PVA were rather similar. It
should be stated that tensile strength of the films increased
with higher hydrolyzation degree PVA. Results of water
repellence and bond resistance to water correlate to each
other. Films with the high hydrolyzation degree as well
high ethylene moieties content PVA showed higher water
resistance. Nevertheless, all samples didnt pass sequence
No. 3 requirements.
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