B O
VIC
VIT NAM
Viện Kỹ thuật nhiệt đới
***
ĐàM XUÂN THắNG
NGHIÊN CứU TổNG HợP Và KHÂU MạCH
DầU HạT CÂY ĐEN ACRYLAT HóA
Chuyên ngành: hóa hữu cơ
Mã số : 62 44 01 14
LUn áN TIếN S hóA HọC
ng dn khoa hn
2. PGS. TS. Nguyn Th Vit Triu
Hà Nội - 2014
LI C
T xin c PGS.TS. n PGS.TS. Nguyn Th Vit
Triu ng d trong suc hin lu
ng c i hc
Vin K thut nhii, tp th t liu cdu nh
ng nghin K thut nhii , tu
kin thun l i dung lu
h cng vin, khuy
trong suc hin lu
lu
ng
L
Luc thc hin tt liu nh
Vin K thut nhii, Vi Vit Nam.
ng ni dung u do
c hii s ng dn cng dn khoa hc liu, kt
qu trong bt k
lu
ng
BNG CH VIT TT
AESO
:
BCDE
: Bis-xycloaliphatic diepoxy
BMF
dehit
BTEAC
: Benzyltrietylamoni clorit
13
C-NMR
CEN
: O-crezol epoxy novolac
DGEBA
: Diglyxydyl ete bisphenol A
DGEDA
: bisphenol-A-diglyxydyl ete diacrylat
DGEDM
: bisphenol-A-diglyxydyl ete dimetacrylat
: D
DV
: D
DOP
: Dioctyl phtalat
D
: D
ET
: D
GMA
: Glyxydyl metacrylat
H4.12.2
oligome monome nbisphenol-A-diglyxydyl ete
dimetacrylat(DGEGMHDDA) = 25/15
1
H-NMR
HDDA
: 1,6-Hexandiol diacrylat
HEA
: Hydroxyetylacrylat
HMBC
: Heteronuclear Multiple Bond Correlation
HSQC
: Heteronuclear Single Quantum Coherence
MAESO
MMA
: Metyl metacrylat
MEXP
: Metyl etyl xeton peroxit
LO
: D
LFA
:
PEPTA
: Pentaecrytritol propan triacrylat
TAS
: Mtriarylsunfonium hecxanfluoroantimonat
TBAB
: Tetrabutylamoni bromit
TEAB
: Tetraetylamoni bromit
TMPTA
: Trimetylolpropan triacrylat
I.184
: -hydroxyl ankyl phenyl xeton
PHA
: Poly(3-hydroxy an
VOAC
: vernonia
VO
vernonia
i
MC LC
1
4
ACRYLAT 4
6
7
8
. 10
11
11
11
11
11
13
13
15
20
26
26
27
36
ii
39
2.1. 39
39
39
39
40
40
40
40
41
41
41
41
44
44
44
2.6.2. 44
45
45
46
47
47
47
iii
59
62
62
66
69
75
3.3.1 76
76
84
84
85
95
112
128
130
131
132
iv
DANH MNG, BIU TRONG LU
Trang
8
12
1
H-
VOAC
17
13
C-
VOAC
18
24
1
H-
13
C-
25
26
27
28
0.
34
quang
quang I.184
41
42
43
43
v
1
H-
54
13
C-
57
65
/mol epoxy = 20/1
70
1
H-
77
1
H-
80
13
-
82
85
sau khi
86
95
96
vi
M
101
106
110
113
114
119
122
124
125
vii
DANH M TH TRONG LU
Trang
1
H-
17
1
H-
17
13
C-
18
13
C-
18
52
53
1
H-
53
1
H-
54
1
H-
2
(glyxerin).
54
13
C-
56
56
.
59
)
.
60
61
.
61
o
C.
62
-1750cm
-1
.
63
viii
acrylat -1080cm
-1
.
65
o
C.
67
o
o
C (c).
69
o
C.
71
o
C.
71
72
o
C.
73
o
C.
74
metacrylic (
o
C.
74
60
o
C.
76
1
H-
77
1
H--6,4 ppm.
79
ix
1
H--5,0 ppm.
79
13
C-
81
82
7.
82
86
88
- 4
89
)
90
)
q
91
91
)
93
)
93
x
96
98
99
quang
100
M
101
M
M
103
M M
104
M M
105
(b).
106
xi
107
nhau
108
nhau trong
109
114
116
117
118
120
xii
121
123
184
124
1
M U
Vt liu kim lophi kim loi m quan tru trong sn
xui sng. S y vt liu kim long c
yu t ng tn tht to ln cho nn kinh t
i, l b bi
t liu kim lo t liu phi kim loi c
ta l n 5 ln so vTn th
t liu phi kim loi
bio v c ta hing 1 t USD m
n cht ca vt liu t mi
o v ch m vt liu
n dt c ch, s dp ph bo v, Hin
dp ph bo vc bio v bng lp ph hu
n bc s dng
ph bim t trng ln [5]ng s dng
n sc khc
bit ngun kiy, vi d
o t th cho ngu n bn
v
M bi
trm trng u to ra, s dng vt liu chng cao,
ng u. tvt liu
u, sn xut p trung gii quyt c hai
v: bn cht lp ph
p chc metacrylat vt liu
polyme compozit, m vt liu bo v ch ng cao. Do
t ho , d tham gia phn ch quang to ra sn
phm chng, kinh t o v ng
2
u tng hp t i thc vu thc v
ra r g i
nhu thc vt acrylat xy ra nhanh, sn pht tt. Hin
nay, vt liu bo v du thc vt c
u t ht ca acrylat
du thc vt ng thi tn dc ngu r tin, s
ng [57]ng dvt li
du thc vt ng khc phc mt s m ca
hp ch th
n v n.
u loa, c, tru, su
u d gii, u
c bit, du c M u c
Bn mng u vi
hoc cao c s dng trc tip hoc bii bng
o n ph ng dng
trong nhic [57].
u khc nghi cu v vt liu bo v,
ng cao rt ln. Vi nguu du thc vt dc
bi u h mt loi d c
c ta, cu, viu lp ph bo v, trang
du thc vt u h
rt n thit.
Lu u tng h ch
c thc hi n gii quy
3
Mc ca lu
- u kin t u h ch
du h t
ng tt.
- dng du ht liu bo v,
ng cao.
i dung u a lu
1. bc ho
nh cu bii du h thu ho
.
u ng ca n, bn cht ca n
phn u hng acrylic hoc nh
u kin tu h
s.
u ng ca bn chu kin
phn n phn ch quang ca mt s h
du h nh u kin ch quang t
sn phm ch.
Lu m n m u, tng quan, thc nghim, kt qu tho
lun, u tham kho.
4
1. TNG QUAN
1.1. LCH S P CH
ACRYLAT
Hp cht p ch
metacrylatp chm monome acrylat, metacrylat,
oligome, polyme acrylat, metacrylat (nha epoxy acrylat , du thc vt
c s dng
ph bi ch to nhi
p chc bit monome quan tr
ch to nha acrylic.
t acrylic lu ch ng phn ng oxy
u ch ng
-hydroisobutyrat. Hin nht
sn xut acrylic Deer Park (M) t 580.000 tBASF (c)
t 270.000 t Dzerzhinsk (Nga) s25.000 t [36].
n t
ng h
c sn xu sn su
Dzerzhinsk Tuy
n mnh m t c ng d
sn xut nh [36, 52].
ng cht l mt
c-, - n xu to ra nhiu
hp cht nha nhit do hay nhit r ch bi t
l hp phn c c s dng trong rt
nhit ph b mt, dt may, cht kt d tng
hc ng dt ty ra, cht
t p th n xut ln). Do vy, vi
5
cng hp ch quan
u, sn xut.
c n ch
acrylai ta s d tng hi nh cng
c vt li
cht quang hc tc sn xut vi quy p lu
33. Do poly(metyl metacrylat) t mi ging vt liu
thu m tr t quan trng trong s i nh
ra, nhu cu v c s d u ch
cng c i sn ph c ng dng
n ch ng cao p da gi i si
81].
c
u tn, tr USD, vi m [94]i
i h ng rn phm
n bng ng cao c s dng trong nhi
vn dy s ng c
ng thi vi s n ca khoa hc k thu d
vt lit dng cung c l
cho nhu cu s d
Th h n ph
oligot
tr thiacrylat (HDDA), trimetylol propan
triacrylat (TMPTAPEPTA). Trong
s di ta nhn thy p cht acrylat tr th
ng da. Ph n s n th h n phm
acrylat th hai s d ng da.
Kt qu c b
nh n m kh
6
n gi c kh t cua
ch m cn thin phm acrylat th h th
hai v n phm n cha
m 3 - n ph
quang ca chi trong sn phn v
i tc bit quan trng trong mt s ng dng
cp ph n bng tia t ngoc ph
n th h n phm
acrylat th p ch
[44, 51].
n 2010-2015, nhu cu th gii vi c d
s nhu cu v acrylic (GAA)
ng khong 5,4 % yu do s d sn xup
thn xuc d ng 3,7% i nhu cu s dng
n xut n xut ln (BASF, Arkema,
r mi ta
m quan tr gii [36, 52].
acrylat
1.2. DNG VT LIU
BO V
Vt liu bo vp ph ht liu bo
v polyme compozit) gt t gia, chn,
vt ling, ch, . Vt liu bo vt liu
c ph mt ca mt v ci thit b mt c
th bn m, chc,
7
mt phn thit yu ca sn phm cu n, thit b,
linh kin, ).
Vt liu bo v ch t t gia h
ch g tp ph trong.
gim
tp ph [5].
1.2.1. dng vt liu bo v
gii
t liu bo vp ph h
quan trt ph bi trong vic bo qun, gi
m m c v ca
vt liu bo v, p ph h6 t 91
t 12 t tr 110 t 6 t tr 69 t
USD vi m 4,3 - 4,8% [40].
Vt liu bo v, p ph ht nhanh v s ng
chng loc s dc sn xu
, . Nh chng, bo v
u v chng loi ci vt liu bo v
bp ph h
Hin nay, doanh thu t n xut vt liu bo vng
p ph ht ph
nn kinh t cc. Trong tng s n xut vt liu bo v, trang
gi
t liu bo v, n nht th gi
110].
8
Bng 1.1. Doanh thu cn xut vt liu bo v,
u th gii
STT
c
Doanh thu (t USD)
1
Akzo Nobel
6,974
14,124
14,577
2
Henkel
c
6,236
9.849
10,888
3
PPG
M
5,566
10,935
10,788
4
Sherwin-Williams
M
5,728
6,521
7,326
5
Dupont
M
3,780
4,300
4,281
6
BASF
c
2,714
3,729
3,956
7
RPM
M
2,556
3,643
3,381
8
Valspar
M
2,713
3,168
3,704
9
Kansai paint
Nht
1,775
2,299
3,250
10
Asian Paints
0,745
1,062
1,830
Trong s n xut vt liu bo v ln nht
gii (bng 1.1 a My s n ca
sn xu ca th ng M.
1.2 dng vt liu bo v
Vit Nam
n khoa h thp, s dng ch yu
vt liu bo vph bing.
Hi yu sn xut nha ankyt, d
du lanh, du tru, d
cn vt liu bo v i h
i h. HCM, Vin K thut nhii, Vin
p, Vin K thu, nh