|
UBEPOL-BR
High CIS Polybutadiene
High CIS Polybutadiene for High Impact Polystyrene
(HIPS)
• UBEPOL-BR is the brand name of High CIS
Polybutadiene produced by using a cobalt
catalyst system.
• UBE process is characterized by its versatility in producing
polybutadiene with different
molecular weight distribution and linearity of molecular
chain.
• There are 6 grades for HIPS: UBEPOL-BR15HB, UBEPOL-BR15H,
UBEPOL-BR15HL, UBEPOL-BR13HB, UBEPOL-BR34HL, and UBEPOL-BR22H.
• UBEPOL-BR15HB, UBEPOL-BR15H, and UBEPOL-BR15HL are different
with respect to
solution viscosity, corresponding to the difference in
the degree of branching.
• UBEPOL-BR13 HB is characterized by the lowest solution viscosity
of the 6 grades.
• UBEPOL-BR34HL is designed to have lower molecular weight and
higher linearity
than UBEPOL-BR15HB.
• UBEPOL-BR22H is designed to have broad molecular weight distribution.
Properties of UBEPOL- BR for HIPS
(The data of other companys' BR are also listed in comparison with
UBEPOL-BR)
| Table 1 Typical
Properties of UBEPOL-BR |
| |
UBEPOL-
BR15HB |
UBEPOL-
BR15H |
UBEPOL-
BR15HL |
UBEPOL-
BR13HB |
| Money
Viscosity (ML1+4,100°C) |
40 |
43 |
43 |
30 |
| Volatile
Matter (wt.%) |
0.3 |
0.3 |
0.3 |
0.3 |
| Ash
Content (wt.%) |
0.05 |
0.05 |
0.05 |
0.05 |
| |
Micro
Structure
(wt. %) |
Cis |
97 |
98 |
98 |
96 |
| Trans |
2 |
1 |
1 |
2 |
| Vinyl |
1 |
1 |
1 |
2 |
| Molecular
Weight & Molecular Weight Distribution |
Mw
(x 104) |
56 |
61 |
57 |
49 |
| Mn
(x 104) |
17 |
21 |
23 |
13 |
| Mw
/ Mn |
3.3 |
2.9 |
2.5 |
3.8 |
| Lineality
of Molecular Chain |
less |
medium |
more |
less |
| 5wt.%
Solution in Styrene |
Solution
Viscosity (cps) |
60 |
92 |
135 |
41 |
| Syrene
Insolubles (wt. %) |
0.005 |
0.005 |
0.005 |
0.005 |
| APHA
Color |
10 |
10 |
10 |
10 |
| Remarks |
Branching
Type Equivalent to A |
Standard
Type |
Linear Type |
Good
Gloss |
|
| |
UBEPOL-
BR22H |
UBEPOL-
BR34HL |
A
(High-Cis) |
B
(Low-Cis) |
C
(Low-Cis) |
| Money
Viscosity (ML1+4,100°C) |
41 |
34 |
44 |
34 |
52 |
| Volatile
Matter (wt.%) |
0.3 |
0.3 |
-- |
-- |
-- |
| Ash
Content (wt.%) |
0.05 |
0.05 |
0.08 |
0.02 |
0.02 |
| |
Micro
Structure
(wt. %) |
Cis |
98 |
98 |
98 |
35 |
35 |
| Trans |
1 |
1 |
1 |
55 |
55 |
| Vinyl |
1 |
1 |
1 |
10 |
10 |
| Molecular
Weight & Molecular Weight Distribution |
Mw
(x 104) |
70 |
51 |
58 |
37 |
42.2 |
| Mw
(x 104) |
15 |
22 |
18 |
15 |
17.4 |
| Mw
/ Mn |
4.7 |
2.3 |
3.2 |
2.5 |
2.4 |
| Lineality
of Molecular Chain |
medium |
more |
-- |
-- |
-- |
| 5wt.%
Solution in Styrene |
Solution
Viscosity (cps) |
202 |
91 |
64 |
87 |
166 |
| Syrene
Insolubles (wt. %) |
0.005 |
0.005 |
0.015 |
0.003 |
0.003 |
| APHA
Color |
10 |
10 |
15 |
10 |
10 |
| Remarks |
Superior
Impact Strength |
Good
balance between Gross and Impact Resistance |
|
|
|
|
Solution Viscosity and Rubber Content
The correlation between rubber content and solution viscosity is given
in Fig. 1.
| Fig. 1 Rubber Cont. in Styrene vs.
Solution Viscosity |
 |
|
Cold Flow
Property of cold flow of UBEPOL-BR is shown in Fig. 2.
| Test Method |
 |
| Fig. 2 Cold Flow of BR |
 |
|
Storage Stability
The change of physical properties of UBEPOL-BR15HB stored for a long
time in shown on Table 2.
Table 2
The Change of Physical Properties of UBEPOL-BR15HB Stored
for a Long Time |
| Properties |
Storage
Time (day) |
| 0 |
86 |
184 |
340 |
380 |
| Mooney
Viscosity (ML1+4, 100°C) |
41 |
41 |
41 |
40 |
41 |
| 5wt.%
Solutionin Styrene |
Solution
Viscosity at 25°C (cps) |
61 |
60 |
62 |
58 |
59 |
| Styrene
Insolubles (wt.%) |
0.005 |
0.006 |
0.008 |
0.008 |
0.007 |
| APHA
Color |
10 |
10 |
10 |
10 |
10 |
|
Application for
HIPS
We conducted the test of HIPS which is produced using the raw polymer
(polybutadiene) as shown on Table 1 under the following polymerization
conditions.
| Polymerization
Condition |
| Pre-Polymerization (at Bulk) |
Characteristics |
| Rubber Cement
|
7 wt. % |
| Temperature |
135°C |
| Reactor |
1 lit.
separable flask |
| Impeller |
Anchor
type |
Condition (1)
Chaintransfer |
n-DM=0.03
wt. % |
Condition (2)
Chaintransfer |
n-DM=0.03
wt. % |
| Catalyst |
PH-3M=0.03
wt. % |
| Polymerization (at Suspension)
|
| Reactor |
1.5 lit.
autoclave |
| Catalyst |
BPO/DCP=0.2/0.2
wt. % |
| Stabilizer for
Suspension |
PVA |
| Temp. x Temp.
|
100°C x
2 hrs 125°C x 3 hrs 140°C x 2hrs |
| (Note) |
| n-DM |
N-Dodecyl
mercaptane |
| PH-3M |
1,1'-Di-(t-butylperoxy)-3,3,5-trimethylcyclohexane |
| BPO |
Benzoyl
peroxide |
| DCP |
Dicumyl
peroxide |
| PVA |
Polyvinyl
alcohol |
|
| Test Method |
| Toluene Insolubles: |
Weight % Toulene Insolubles
in HIPS |
| Swelling
Index: |
(Wet
Weight/Dry Weight) of Toulene Insolubles |
| MEK/Acetone
Insolubles: |
Weight
% of MEK/Acetone Insolubles in HIPS
(MEK / Acetone = 50/50) |
| Melt
Flow Index: |
ASTM
D1238, 200°C, 5kg |
| Tensile
Strength: |
ASTM
D638 |
| Elongation: |
ASTM
D638 |
| Izod
Impact Strength: |
ASTM
D256, Notched, Thickness of Specimen, 3.16 mm |
| Gloss: |
JIS
Z8741 Incidence Angle 60° |
| Vicat
Softening Point: |
ASTM
D1525 |
| Rubber
Particle Size; |
|
| Equipment: |
Caulter
Counter, TA II Model |
| Dispersion
Medium: |
Dimetlyl
Formamide |
| Electrolyte: |
Ammonium
Thiocyanate |
| Aperture
Tube: |
30µ |
|
Characteristics of HIPS in UBEPOL-BR15HB,
UBEPOL-BR15H, and UBEPOL-BR15HL
• BR15HB is characterized by the
highest branching of these 3 grades and is adapted by
many PS manufacturers.
• BR15HL is a linear type of polymer with high-solution viscosity.
• When enlarging the dispersed rubber particle size in HIPS,
this polymer can be useful
for PS manufacturers.
• The characteristics of BR15H lie in between those of BR15HB
and BR15HL.
Physical Properties of HIPS
Polymerization was performed by (1) and (2) of pre-polymerization
condition, and the physical properties of the obtained HIPS are
shown on Table 3.
| Table 3. Physical
Properties of HIPS |
| Pre-
polymerization Condition |
Grade
|
Swelling
Index |
MEK/
Acetone Insolubles (wt.%) |
Rubber
Particle Size (µ) |
Tensile
Strength (MPa) |
| at
yield |
at
break |
|
(1) n-DM = 0.03wt.%
|
UBEPOL-BR15HB |
10.9 |
23.0 |
2.1 |
30 |
29 |
| UBEPOL-BR15H |
10.7 |
23.3 |
2.5 |
29 |
29 |
| UBEPOL-BR15HL |
10.6 |
23.5 |
2.7 |
29 |
30 |
| A
(High-Cis) |
10.8 |
22.8 |
2.2 |
30 |
29 |
| B
(Low-Cis) |
10.0 |
24.7 |
1.8 |
31 |
30 |
| C
(Low-Cis) |
9.9 |
26.2 |
2.2 |
32 |
31 |
|
(2) n-DM =0.03wt.%PH-3H=0.03wt.%
|
UBEPOL-BR15HB |
13.3 |
23.4 |
0.9 |
34 |
30 |
| UBEPOL-BR15H |
12.9 |
23.5 |
1.0 |
33 |
30 |
| UBEPOL-BR15HL |
12.6 |
24.1 |
1.0 |
33 |
29 |
| A
(High-Cis) |
13.2 |
23.0 |
0.9 |
34 |
30 |
| B
(Low-Cis) |
12.1 |
25.3 |
0.8 |
35 |
32 |
| C
(Low-Cis) |
11.9 |
26.4 |
0.9 |
36 |
33 |
|
| Pre-
polymerization Condition |
Grade
|
Elongation(%)
|
Izod
Impact Strength (J/m) |
Gloss |
Vicat
Softening Point (°C) |
Melt
Flow Index
(g/10 min.) |
|
(1) n-DM =0.03wt.%
|
UBEPOL-BR15HB |
22 |
76 |
59 |
101 |
3.6 |
| UBEPOL-BR15H |
23 |
75 |
56 |
101 |
3.5 |
| UBEPOL-BR15HL |
25 |
75 |
51 |
101 |
3.6 |
| A
(High-Cis) |
22 |
75 |
59 |
101 |
3.5 |
| B
(Low-Cis) |
20 |
66 |
63 |
101 |
3.5 |
| C
(Low-Cis) |
20 |
64 |
58 |
101 |
3.5 |
|
(2) n-DM =0.03wt.%PH-3H=0.03wt.%
|
UBEPOL-BR15HB |
7 |
59 |
78 |
101 |
2.8 |
| UBEPOL-BR15H |
8 |
70 |
80 |
101 |
2.7 |
| UBEPOL-BR15HL |
8 |
74 |
83 |
101 |
2.7 |
| A
(High-Cis) |
7 |
58 |
79 |
101 |
2.8 |
| B
(Low-Cis) |
6 |
49 |
85 |
101 |
2.8 |
| C
(Low-Cis) |
6 |
51 |
83 |
101 |
2.8 |
|
Low temperature Property
of HIPS
Dependence in Fig. 3. Low temperature property of HIPS modified
by high cis BR is better than that modified by low cis BR.
| Fig. 3 Temperature vs. Izod Impact
Strength.
|
 |
| Note: Specimens
were kept at test temperature for 5 hrs. |
|
Dissolving Time
UBEPOL-BR13HB has such characteristics as low solution viscosity and
short dissolution time in styrene monomer. Fig. 4 shows the transient
behavior of UBEPOL-BR13HB form the time when a certain amount of rubber
is put into styrene monomer and is stirred until its solution viscosity
increases and becomes constant.
| Fig. 4-1
| Fig. 4-2
|
 |
 |
| Dissolving
Time of BR in Styrene |
Dissolving
Time of BR in Styrene |
|
Change of Motor Current During Pre-polymerization
The correlation between conversion ratio and motor current in agitator
is given in Fig.5. As UBEPOL-BR13HB is of low molecular weight and
a branching type, its viscosity of polymer cement is low up to 6-7%
of conversion ratio where a phase inversion takes place, which makes
it possible to control to make rubber particles size smaller so that
a type oh high gloss HIPS can be obtained. In the case of UBEPOL-BR13HB,
stirring power consumption is less for polymerization of HIPS.
| Fig. 5
|
 |
| Conversion
vs. Motor Current |
|
Physical Properties of HIPS
Polymerization was performed by (1) and (2) of pre-polymerization
condition, and the physical properties of the obtained HIPS are shown
on Table 4.
| Table 4. Physical
Properties of HIPS |
| Pre-
polymerization Condition |
Grade
|
Swelling
Index |
MEK/
Acetone Insolubles (wt.%) |
Rubber
Particle Size (µ) |
Tensile
Strength (MPa) |
| at
yield |
at
break |
(1)
n-DM=0.03wt. % |
UBEPOL-BR13HB |
11.2
|
22.1 |
1.6 |
31 |
30 |
| UBEPOL-BR15HB |
10.9 |
23.0 |
2.1 |
30 |
29 |
|
(2)
n-DM=0.03wt. %
PH-3H=0.03wt.%
|
UBEPOL-BR13HB |
13.7
|
21.9 |
0.8 |
35 |
31 |
| UBEPOL-BR15HB |
13.3 |
23.4 |
0.9 |
34 |
30 |
|
| Pre- polymerization
Condition |
Grade
|
Elongation(%)
|
Izod
Impact Strength (J/m) |
Gloss |
Vicat
Softening Point (°C) |
Melt
Flow Index (g/10 min.) |
(1)
n-DM=0.03wt. % |
UBEPOL-BR13HB |
20
|
72 |
68 |
101 |
3.6 |
| UBEPOL-BR15HB |
22 |
76 |
59 |
101 |
3.6 |
|
(2)
n-DM=0.03wt. %
PH-3H=0.03wt.%
|
UBEPOL-BR13HB |
7
|
53 |
82 |
101 |
2.8 |
| UBEPOL-BR15HB |
7 |
59 |
78 |
101 |
2.8 |
|
Characteristics of HIPS
in BR13HB
• BR13HB is characterized by its low solution viscosity compared
with
conventional grades.
• Short dissolution time in styrene monomer
• Small power consumption necessary for agitation for polymerization
in HIPS
manufacturing process
• High rubber content, because of low solution viscosity, produce
HIPS of a higher
impact strength
• It is easy to make small rubber particles in HIPS
Characteristics of HIPS in BR22H
• BR22H is characterized by its broad molecular weight distribution,
called a
"binary polymer".
• The properties of HIPS modified by BR22H are extremely good,
and better than as
performed by (1) and (2) of pre-polymerization condition.
Molecular Weight Distribution
Molecular weight distribution of UBEPOL-BR22H is shown in Fig 6
in comparison with UBEPOL-BR15HB and B (Low cis).
| Fig. 6
|
 |
| Molecular Weight
Distribution by Gel Permiation Chromatogram. |
|
Physical Properties of
HIPS
Polymerization was performed by (1) and (2) of pre-polymerization
condition, and the physical properties of the obtained HIPS are
shown on Table 5.
| Table 5. Physical
Properties of HIPS |
| Pre-
polymerization Condition |
Grade
|
Swelling
Index |
MEK/
Acetone Insolubles (wt.%) |
Rubber
Particle Size (µ) |
Tensile
Strength (MPa) |
| at
yield |
at
break |
(1)
n-DM=0.03wt. % |
UBEPOL-BR22H |
11.3 |
23.1 |
2.6 |
27 |
28 |
| UBEPOL-BR15HB |
10.9 |
23.0 |
2.1 |
30 |
29 |
| B
(Low-Cis) |
10.0 |
24.7 |
1.8 |
31 |
30 |
|
(2)
n-DM=0.03wt. %
PH-3H=0.03wt.%
|
UBEPOL-BR22H |
13.5 |
23.6 |
1.0 |
33 |
29 |
| UBEPOL-BR15HB |
13.3 |
23.4 |
0.9 |
34 |
30 |
| B
(Low-Cis) |
12.1 |
25.3 |
0.8 |
35 |
32 |
|
| Pre- polymerization
Condition |
Grade
|
Elongation(%)
|
Izod
Impact Strength (J/m) |
Gloss |
Vicat
Softening Point (°C) |
Melt
Flow Index (g/10 min.) |
(1)
n-DM=0.03wt. % |
UBEPOL-BR22H |
30 |
79 |
54 |
101 |
3.5 |
| UBEPOL-BR15HB |
22 |
76 |
59 |
101 |
3.6 |
| B
(Low-Cis) |
20 |
66 |
63 |
101 |
3.5 |
|
(2)
n-DM=0.03wt. %
PH-3H=0.03wt.%
|
UBEPOL-BR22H |
15 |
78 |
80 |
101 |
2.8 |
| UBEPOL-BR15HB |
7 |
59 |
78 |
101 |
2.8 |
| B
(Low-Cis) |
6 |
49 |
85 |
101 |
2.8 |
|
Physical Properties of
MIPS (Medium Impact Polystrene)
Polymerization was performed in different stirring rates under pre-polymerization
condition (1)(2.5 wt. % rubber content) and the characteristics
of the obtained MIPS are shown on Table 6. The correlation between
Izod impact strength and rubber particle size is shown in Fig. 7
and correlation between Elongation and Rubber particle size is shown
in Fig. 8.
| Table 6. Physical
Properties of MIPS |
| Grade
|
Stirring
Rate (rpm) |
Swelling
Index |
MEK/
Acetone Insolubles (wt.%) |
Rubber
Particle Size (µ) |
Tensile
Strength (MPa) |
| at
yield |
at
break |
| UBEPOL-BR22H |
600 |
12.7 |
7.3 |
1.4 |
41 |
39 |
| 500 |
12.8 |
7.8 |
1.6 |
38 |
37 |
| 400 |
13.0 |
8.2 |
2.1 |
36 |
36 |
| 300 |
13.3 |
8.8 |
2.8 |
36 |
36 |
| UBEPOL-BR15HB |
500 |
12.9 |
7.3 |
1.3 |
-- |
41 |
| 400 |
12.7 |
7.8 |
1.5 |
-- |
39 |
| 300 |
12.7 |
7.9 |
2.0 |
40 |
39 |
| 200 |
13.0 |
8.6 |
2.7 |
39 |
38 |
|
| Grade
|
Elongation(%)
|
Izod
Impact Strength (J/m) |
Gloss |
Vicat
Softening Point (°C) |
Melt
Flow Index(g/10 min.) |
| UBEPOL-BR22H |
5 |
29 |
96 |
101 |
8.3 |
| 5 |
33 |
94 |
101 |
8.2 |
| 8 |
38 |
92 |
101 |
8.0 |
| 10 |
42 |
87 |
101 |
8.1 |
| UBEPOL-BR15HB |
3 |
22 |
97 |
101 |
8.1 |
| 4 |
28 |
94 |
101 |
8.3 |
| 6 |
33 |
92 |
101 |
8.3 |
| 6 |
36 |
80 |
101 |
8.0 |
|
| Fig. 7
| Fig. 8
|
 |
 |
| Rubber
Particle Size vs. Izod Impact Strength |
Rubber Particle Size vs. Elongation |
|
Characteristics of HIPS
in BR34HL
• BR34HL is characterized by its lower molecular weight and
higher linear molecular chain
compared with BR15HB. The properties of HIPS modified
by BR34HL are significantly
better than the other grades with respect to the balance
between gloss and impact
resistance.
Physical Properties of HIPS
Polymerization was performed in different stirring rates under pre-polymerization
condition (2) and the characteristics of the obtained HIPS are shown
on Table 7.
The correlation between glass and rubber particle size is shown
in Fig. 9 and the correlation between gloss and Izod impact strength
is shown in Fig. 10
| Table 7. Physical
Properties of HIPS |
| Grade
|
Stirring
Index |
Swelling
Index |
MEK/
Acetone Insolubles (wt.%) |
Rubber
Particle Size (µ) |
Tensile
Strength (MPa) |
| at
yield |
at
break |
| UBEPOL-BR34HL |
500 |
12.7 |
24.0 |
0.94 |
34 |
30 |
| 400 |
11.9 |
25.2 |
1.23 |
31 |
30 |
| UBEPOL-BR15HB |
500 |
13.3 |
23.4 |
0.89 |
34 |
30 |
| 400 |
12.5 |
24.4 |
1.18 |
33 |
30 |
| B
(Low-cis) |
500 |
12.1 |
25.3 |
0.82 |
35 |
32 |
|
| Grade
|
Elongation(%)
|
Izod
Impact Strength (J/m) |
Gloss |
Vicat
Softening Point (°C) |
Melt
Flow Index(g/10 min.) |
| UBEPOL-BR34HL |
9 |
69 |
86 |
101 |
2.8 |
| 43 |
79 |
80 |
101 |
2.7 |
| UBEPOL-BR15HB |
7 |
59 |
78 |
101 |
2.8 |
| 34 |
74 |
74 |
101 |
2.6 |
| B
(Low-cis) |
6 |
49 |
85 |
101 |
2.8 |
|
| Fig. 9
| Fig. 10
|
 |
 |
| Stirring
Rate vs. Gloss |
Izod Impact Strength vs. Gloss |
|
|
