Confidential 2013.11.

19

DENKR
O€['KI KAGAKU KOGYO XAR.'sHIKI KA'SHA
TR-13'1103

Attn : Thai Plastic and Chemicals Public Company Limited / Thailand

DENKA POVAL for Vinyl Chloride Polymerization

Denki Kagaku Kogyo Kabushiki Kaisha

Omi-Plant
First Organic Department
PVA Development

Produ-ction Flow and SI;t:ru ctu

ctu re Of PVA
H
CHr=QP
-l
c)H, -c- F-l
o Polymerization o ?l
I

I
C=O
I
CH,
VinylAcetate
t g=o
C=t

:ly V inyl,Acetate
I

CHt
CH )
I

H X Hydrolysis Degree
-[.r, F
gl-lr-9 (Saponification Degree)
m
o HD= x100
I m+n
C=O
LO I
CHu
X Polymerization Degree
tO,-- m + n
Poly Vinyl Alcohol (PVA)
z
 DENKA POVAL for PVC Polymerizalion
100

G
:-o 90

UE
o
o
!-
d)
6UU
.2
u)

o
L
!
J-
:'70

1000 1500 2000

Polymerization Degree

Properties of Typical Grades of DENKA POVAL

for PVC Polymerization

Vofatiles (%) < 5.0 < 5.0 < 5.0 < 5.0
Viscosity r) (mPa.s) 37-43 44-55 9.0-13.0 6.0-9.0
Hydrolysis (mol%) 78. 78.5-80.5 70.5-74.5 70.5-74.5
2)
PH 5.0-7.0 5.0-7.0 5.0-7.0 5.0-7.0
Sodium Acetate f/") s 0.5 < 0.5 < 2.0 < 2.0
nCrL
1) 4% aqueoussolution, 20"C, JIS K-6726
2) 4%aqueous solution, 25'C
 Comparison with Competitor's Grades

DENKA (Japan)

--r

Kuraray (Japan) ^';: 424H L type

Nippon Gohsei (Japan) KH17 KH20 KP type

g0 Alcotex 72'5
synthomer (u.K.) Atcotex
Alcotex 872

INTRODUCTION of W Type
(Polymer Structure of W-type)
gHs
t
Ac :
-C-.\b

Standard PVA

(Random Distribution of Acetate Groups)

(w-20N, w-24N)

(Block Distribution of Acetate Groups)

 30L PVC Reactor (Outline Drawing)
IPaddle impeller (3stages) ) IPfaudler impeller)

Conditions to Synthesis of PVC with W type

)duilitit!'J
Stirre Paddle (650rpm) Ffaudler {550rpm}
Temperature ("C) 57.5 57.5
Reaction Time (hr) 4 4
Pressure (Finished) (MPa) 0.765 0.765
)ttetuc
Water (kg) 14 14
VCM (kg) 10 10
Initiator (%A/CM)
BND 0.046 0.046
CND 0.010 0.010
Dispersant (o/"NCM) o@@ o@@
Primal 0.120 0.104 0.120 0.120 0.104 0.120
MC tl 0.016 0.016
Secondary z)
0.020 0.020
'1) Methyl Cellulose, 2) Hydrolysis 39mol%
 lnitiator
Trade Name 1)
Percumyl ND Perbutyl ND
(cND) (BND)
Cumyl peroxyneodecanoate r-Butyl peroxyneodeca noate
Structural Formula
?r, ? ?r, ?t'
CH3-C-O-O-C-C-C6H13
? ?t'
?-o-o-c-?-.rr,',
CHs CHs GHa CHs

Molecular Weight 306.45 244.38

Half-life Data z)

1 min 94.0 "c 103.5 "C

t hour 55.0 "C 64.9'C
1 Ohour 36.5 "C 46.4"C
Activation Energy 105.3 kJ/mol 112.0 kJ/mol

1 ) NOF Corporation, (Japan) http://www.nof.cojp/english/index.html

2) The reactivity of an organic peroxide is given by its halfJife at various temperature.
Pyrolysis in Benzene, concentration: 0.10 mmol/1.

Performance of W-20h1
as Primal Dispersant (Paddle)
)VA recipe PVA only PVA/MC=87/13 with secondarv
I samnle name W-2ON other's W-2ON oiher's W.2ON of har's
rvc Pantcte slze 4-c_!lH_q!_qn v.4 u.4 0.2 o.6 v.z u.4
% 180um on 14.8 21.2 8.0 9.2 19.3 23.0
150um on 22.4 26.4 19.2 .:|"9..?- ."-q9,L"- ""-"q.:!, "_"
-
1009m on 45.6 38.8 53.4 52.0 41.4 38.1
75Um on 14.2 11.0 16.6 16.2 8.0 6.6
75um nass 2.6 22 2.6 2.8 1.0 0.6
Average pant"t"
llm 140 148 132 132 149 154
Distribution um * 63 b4 52 53 57 57
Bulk densitv lo/mll 0.513 0.491 0.481 0.497 0.479 0.477
Frsn eye ,mtn z4v z5z
!min 184 172 33 95 1 1
/min 4 6 4 3
CPA ** ohr ln=21 15.1 17.5 19.8 18.7 24.2 24.4
* d(80%)-d(209il
** PVC,/D OP,/stabili zer / luh ric ants /TO2,zcarbon= 1 00,/50 / 2 / O. B /
i 0. 4 / 0.04lphrl
roll temperature 150 Centigrade, lBrpm, pieces in 100cm2
*** plastic:zer: DOP

rr . i n l""a-{l84\,.
Cf A , ,Jf,, 'lL'6\+'q"Yt- f)ea
 l

Performance of W-20N
as Primal Dispersant (Pfaudler)
PVA recipe PVA onlv PVA/MC=87/13 with secondarv
| <rmnla W-2ON other's W.2ON other's W-2ON other's
)VG .LU 't,4
Particle size igllH!:.n.9n. 0.6 u.6 u.4 u,4
% 160Fm on 16.0 16.2 11.2 20.4 11.8 24.5
1509m on 26.2 25.3 26.1 28.3 35.2
100um on
"4L!i'"' "g-,{
43.4 42.3 35.8 48.1 33.9
75gm on 11.4 12.8 13.4 9.4 10.2 9,?
75um pass 2.2 2.6 3.8 2.6 12 o8
Averaqe particle
um 144 144 140 152 143 158
stze
Distribution um * 60 63 59 62 53 56
Bulk densitv (q/ml) 0.466 o.457 o.475 0.489 0.459 0.457
Fish eye * 3min 368 848
5min 100 136 152 352
Tmin 13 35
5
"19 "

CPA ** phr ln=21 18.1 17.9 18.7 18.7 23.4 22.9

+ d(809;)-d(20%)
++ PVC,/DOP,/stabilizer/lubricants,/fiO2/car6on:100/50/2/0.8/0.4/0.04lphrl
roll temperature 150 Centigrade, lBrpm, pieces in 100cm2
+++ olasticizer: DOP

Performance of W-X€ru
as Primal Dispersant (Paddle)
PVA recipe PVA only PVA/MC=87/13 with secondary
| <rmnla W-24N r)f her's W-24N other's W.24N olher's
|-antcte stze u.b u.b 't.u 't.u 0.4 0.2
Pr vPEr r %
{?-uIqr__o_ll
l-9-orn-g-n - -ad.i
is:.4 E.A 9.2 11.6 ic.2
l50um on 24.5 22.6 13.2 14.5 21.8 27.5
l00um on 43.0 42.6 51.0 qg,? 52.0 44.7
l-9u"n"p-n 10.6 12.2 22.8 21.7 13.2 8.8
75rrm nacs 26 AL 36 3.4 1.0 0.6
AVerage pant"t"
lra 144 142 126 128 136 146
Dislrihulian rrm * 64 66 55 56 53 58
Bulk densitv lo/mll 0.488 0.497 0.488 o.482 0.480 0.477
Fish eye * 3min 6C6 c1z
5mtn 17 28 65 57 10 6
Tmin 0 1 1 1 1 1
CPA * phr {n=21 16.9 16.6 18.6 17.9 21.8 21.6

xx PVC/DOP/stab)) zer/lubricants/fio2/ carbon=100/ 50/2i0.8i0.4i0.041phr1

roll temperature 150 Centigrade. 18rpm, pieces in l00cm2
*** plasticizer: DOP
 l

INTRODUCTION of MP Typq qN'

(fVlolecular Structure of MP type)

l2s

,---3''-'** -r
L
o'y!-L:*P:19-!c-=c-l-i - L--D9-*1"--Brg!9:c)
r
i
t

=*S
End-group
Solvent or Initiator or VinytncetaL
1;16*fu--1
i eno-group i

yOru-4

/ ct
,-- a\=lIC- L -ci{

lmages of Suspension
Polymerization with MP type

MP-10 (R) Other's

1L
I

lmage of strength i
at skin layer Graft point with PVC
(wider is strong)

14
 Formation of PVG Particles
MP.1O Other

-^, O 0-''",.
lmage 't '\oc
Qt 1/ ll l^' ir
---::€ O f\
g.,;-- ''L- ('
Graft Point Many (Random in Chain) Few (Terminal of Chain)
Skin Layer Hard & Stable Soft & unstable
Frequency of
Coalescence and Low & Stable High & unstable
Re-dispersion
among Particles

SEM lmages of PVC Particles

' Surface Fractured lmage

MP-10

other
 Difference of function of MP-10(R)
and PVC particle formation
. Pores will be created In uniform system and
less irregular big pores or hollows on the
surface. Network of pores reaches to the
surface of aggregated PVC particle
r IMP-10(R) will promote stable formation of
relatively smaller droplets and domain
particles.
--) Low CPA but better fish eye characteristics
and higher strippability

Effect of Modifier Amount in MP-1 0

for PVC Particle Size
Primal Particle

J.U
=
=-

.& 2.0
@
o
EL
1.0
(E
(L
Low

('tttt1l rr I u I erl Pu rti cl r

 Conditions of PVC Polymerization
IPaddle impeller(3stages) )
t,Q254 4
)Condition '

Stirre 650rpm
Temperature ("c) 57.5
K Value 64-66
Reaction Time (hr) 4
Pressure (Finished) (MPa) 0.765
lJ)
)Beclpe (1) (21 s
r f-
ct)
N
Water (kg) 14 12
VCM (kg) 65
PVA (%rucM) 0.05-0.16
In itiato r (%rucM)
BND 0.046
CND 0.010
{D"l
ii
il
i-j
luz 19

Resu/fs of PVC Polymerization

n [i-,1
+Tv ,/' Water/VC M='l2l Skg, PVA only
Test No. 1 2 3l 4 5 6 7 8 9 10

PVA
(%A/CM) 0.050 0.065 0.100 0.065 0.080 0.100 0.120 0.160 0.100 0.160
Particle %)
Size 250pm on 2.0 0.8 0.2 18.8 1.0 2.0 0.2 0.2 20.0 0.8
180pm on 16.6 5.0 '1,2 34.2 12.0 12.O 1.8 1.4 36.4 9.2
150pm on 25.3 '13.2 4.8 19.2 2',t.0 17.8 8.6 6.2 16.8 '17.2
100pm on 46.3 57.O 52.',| 23.8 54.4 48.0 61.9 53.2 21.0 46.4
75pm on 8.8 21.6 37.7 3.6 10.8 18.2 25.3 35.0 5.4 22.8
75pm pass 1.0 2.4 4.0 0.4 0.8 2.0 2.2 4.0 0.4 3.6

Average (pm) 144 125 112 186 138 135 120 113 '192 128
dro-dro (pm) 60 46 40 105 53 63 39 41 110 60
B.D. (g/ml) 0.475 0.456 0.461 0.472 0.464 0.453 0.465 0.454 0.445 0.397
CPA (phr) 27.5 28.4 25.3 27.4 28.2 29.7 26.6 27.7 29.3 33.4
Fish (counts
Eye /100cm2)
3 min
14 I 5 59 14 6 4 '17 14 4
2 0 0 4 0 0 0 0 0 0
5 min
0 0 0 I 0 0 0 0 0 0
7 min
 PVC Properties of DOH 70-72% type
57.5"C, Water/VCM=1Z5kg, DOH 70-72% only

250 40

E
o
200
o
(L b X
o
@ o MP-10
.! At
@
o
150 Y30 . MP-10R
o .L X
o v,. rLB
E a ,' A
(!
o '€", :.. u.t " AL9
o a 4.,
A L1O
Ht roo 25
X Alcotex 72.5
x
x Alcotex B72

50 20
0.00 0.05 0.10 0.15 0.20 100 150 200 250
PVA ("/"^/cM) Average particle size of PVC (Um)

21

Performance of ffiP*t * and IWP -l*re

as Primal Dispersant
Water/VCM=1416 kg
Test No L 7 I 9
*ll:,t!1.
PVA C) MP-1OR Alcotex B-72
#85X62
{o/JVCMt
-
g,9gz. . l.
"9,,0-_e""2. . I _ _o-,lq* . .9,957_. 0.070
^6.j.4' "q.,992.."
oosz I ot'tz I otao
PVA O B-24 B-24
(%/vcM) o.ooalo.orglo.ore 0.008 0.010 0.013 o.oralo.orelo.ozo
'orso
Total o.os6 |tl o.ioo.'f-ii.izo 0.065 0.080 0.100 o.ib.d"I o.izii
|
*li t.,:)!it..,i a'l t li
Hydrolysis (mol%) 71.7 72.0 72.4

*8,.,,1r. .:l !'1, tt, !t,.,.';

Particle Size l%l
250pm on 13.8 0.4 0.2 0.4 o.2 0.0 0.2 0.2 0.2
180pm on 29.3 b.b 3.8 5.2 1.6 1.4 3.2 1.2 0.8
150pm on 20.2 16.6 16.9 11.4 6.0 4.8 18.4 8.8 8.8
100pm on 31.1 57.4 56.0 61.6 61.4 55.4 61.0 50.2 55.3
75pm on 5.2 17.2 20.5 19.6 28.2 34.8 16.2 27.O 30.9
75pm pass 0.4 1.8 2.6 1.8 1A 1.0 2.6 4.0
Average (pm) 169 13'l 127 126 'A
117 113 131 119 'I'I b
Distribution (um) 98
'o.ie2 4A 48 42 38 38 44 40 44
gutk '6i:ti5, -o.add -it.46t -
Densitv (qt!!!) N LR) ri aqii- n ran N LLR 6 Aa)
Fish Eye (counU1O0cm'?)
3min 34 4 4 1 2 0 7 14 3
5min 0 0 0 2 0 2 0 0 0
Tmin o 0 0 0 0 u n n
CPA (phr) 26.8 25.4 25.5 25.1 23.7 22.2 27.6 28.1 24.6

Denka Poval B-24.. - . Hvdrolvsis = 86-89mol%, Viscositv = 40-48mPa.s zz

t'rt!.L' fLams''agr Ab e+-r1l{uw = ? f U

 Performance of IVIP-10 and MP-1 0R
as Primal Dispersant
200

E
180
=. a
o 160
.N
o . MP-10R
o
.9 140 r MP-10
L
(E
,t A
(L o a Acotex 872
o 120 lan
ct)
Cl I
o
100

80
0.05 0.10 0.1s

Total PVA (7"/VCM)

SEM lmages of PVC Particles

Prepared by MP-1 0 I B-24

MP-10 = 0.057 %/VCM 0.070 %/vcM 0.087 %/vcM

B-24 = 0.008 %IVCM 0.010 %/vcM 0.013 %/vcM Z1
 SEM lmages of PVC Particles
Prepared by Alcotex E-72 I B-24

Af cotex 872= 0.O87 %IVCM 0.112%NCM

B-24 = 0.013 %/VCM 0.016 %/vcM

Pore size distribution

3.0

IE 2.s 4 . MP-10,/MC
jll
l+ Ncotex72.5.zMC
i

E,O
6
o 1.5
o
o-
,'.0 ;{
E
o
fo '^,.
o.s

0.0
( /F\* )j 0.50
100

Pore Size (pm)

d o.ao
o
E

I o.so
o
o
L 0.20
F
o
.E 0.10
o
0.00

Pore Size (Fm)

20
 lmage of Porosity distribution
Conversion

-2% MP-10 Alcotex

Water (porosity)

- {D7"
PVC particle
Waler

Yr/alEf
V I
Porosi0t sharp broad
- 90% distribtrtion;

Build-up of structure VCM droplet

DENKA POVAL for VCM Polymerization

DENKA POVAL
8006-type
Grade B-24 W-2ON W.24N
Appearance granure granure granule gra nule gra nure

Volatile matter (wto/o) <qn <4n <qn <cn <qn

Hydrolysis degree (molo/o) 86.0-89.0 78.5-80.5 78.5-80.5 70.5-74.5 70.5-74.5
Sodium acetate (wt%) <1 n <nq <nq <tn <)n
pH (4o/o,25"C) 5.0-7.0 5.0-7.0 5.0-7.0 5.0-7.5
Viscosity (4oh,20"C) (mPa's) 40-48 37-43 44-55 9-1 3 6-9
Absorbance (0.2%) (ABS)
280 nm 0.80-1 .30 0.40-0.70
325 nm 0.08-0.20 o.o4-o 14

Competitions t I t t
Kuraray (Japan) 224 420,420H 424H 18, 19. L1 0. 111

Nippon Gosei (Japan) GH-20 KH-l7 KH-20 KP-06R, KP-O8R

KA-800, KX-310
Japan VAM & Poval (Japan) JP-24 JL-22E JL-25E
Synthomer (UK) 8847 Alcotex 80 Alcotex 72.5
Alcotex B72
Ineos (Belgium) PA4 PA6

[FNKN
28
 TR No. 150606

Denka (2015.06.1 0)

Attn.: TPC Vina Plastic & Chemical Corp., Ltd. / Vietnam

Comparison Data between DENKA POVAL W-20N and Gohsenol KH-17

1. PVA Sample
1) DENKA POVAL W-20N
2) Nippon Gosei Gosenol KH-17

2. Comparison of Basic Property

able 1 Comparlson ot Basic Propertres of W-20N and KH-

Test No. 1 2
Suspendinq Aqent VV-ZUN Kf1-1 /
Basic Properties
Hydrolysis Degree t"/;, 78.5 - 80.5 78.5 - 81.5
Viscosity (4o/o, 20"CIm Pa' s 37 -43 32-38
Product Shape Granule Powder

Comparison Test Results on VCM Polymerization

1 ) Polymerization Conditions

e Type of PVC See Below Table

@ Ratio of VCMWater
/ 100 | 140

2) Comparison Test Results

Table 2 Comparison Test Results of W-20N

-ZUN Aand KH-17
Test No. 1 2 3 4
Tvpe of PVC P-1 UUU I-IUU
Suspending Agent W-2ON KH-17 W-2ON KH-17
Addition Amount [ppmA/CMl 1,200 1,200 800 800
Polymerization Conditions
Size
Reactor tll 30 30 30 30
Agitator Paddle Paddle Paddle Paddle
Rate
Rotation lrpm 650 650 650 650
Temoerature f"c 57.5 57.5 66.8 66.8
PVC Properties
(D50)
Particle Size [Un 140 148 180 185
D20)
(D80 - lum 63 64 116 120
Density
Bulk [g/ml] 0.513 0.491 0.541 0.569
cPA [PHR] 16.1 17.5 10.4 8.6
Fish Eye
3 min [piece] >5000 >5000 >5000 >5000
5 min [piece] 184 172 784 864
7 min loiecel 4 6 5 10