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NGHIN CU NH HNG CC YU T N PHN NG
TNG HP KEO POLYPHENOL FORMALDEHYDE
T POLYPHENOL V KEO L TRM
A STUDYING THE INFLUENCE OF ELEMENTS ON THE REACTION TO
FORM POLYPHENOLS FORMALDEHYDE PLYWOOD ADHESIVE
FROM ACACIA AURICULIFORMIS BARKS POLYPHENOL

SVTH: Nguyn Trng Tin
Lp 06SHH, Khoa Ha, Trng i hc S Phm
GVHD: PGS.TS. L T Hi
Khoa Ha, Trng i hc S Phm

TM TT
Keo polyphenols formaldehyde l hng thay th tim nng cho keo dn g phenol
formaldehyde, loi keo c ngun gc t du m, mt ngun ti nguyn t nhin c hn.
Polyphenols chit tch t v cy keo l trm va c kh nng thay cho phenol trong phn ng to
keo dn, va l ngun nguyn liu sch, phong ph. Chnh v th, mc ch ca bi bo l tin
hnh nghin cu nh hng ca cc yu t n phn ng tng hp keo polyphenols
formaldehyde t ngun polyphenols v keo l trm. Kt qu tm c cc iu kin ti u cho
phn ng trng ngng to keo polyphenols formaldehyde v chng minh c kh nng dn g
ca sn phm to thnh.
ABSTRACT
Polyphenols formaldehyde adhesives are potential substitutes for phenol formaldehyde
wood bonding adhesives which are derived from petroleum, a finite natural resource.
Polyphenols extracted from acacia auriculiformi bark both replaces the phenol in the reaction to
form plywood adhesive and is clean, plentiful raw materials. The aim of this study, therefore, was to
reseach into the influence of the elements on the reaction which to form polyphenols
formaldehyde adhesive, with polyphenols extracted from acacia auriculiformi bark. As the result,
we found the optimal conditions to the reaction of polyphenols with formaldehyde and using the
product as plywood adhesive.
1. t vn
Trong cng nghip sn xut mt lng ln phenol, ngi ta c th chit tch
phenol t nha than m hay tng hp phenol t benzen bng cc con ng khc nhau.
Theo thi gian, cc ngun nguyn liu dn dn tr nn khan him, cn kit. Ngun
polyphenols tch t v cy keo l trm (tn khoa hc l Acacia auriculiformi) v cy ph
thi t qu trnh khai thc g l s la chn tt gii quyt vn trn.
Polyphenols v keo l trm cha lng ln tanin ngng t, chng l polyflavonoid,
c to thnh t 5 11 n v monoflavonoid. Mi monoflavonoid c hai vng phenolic
c ni bi d vng [1, 3] nn tanin polyflavonoid c th phn ng vi formaldehyde
tng t hon ton phn ng ca phenol vi formaldehyde. Bn cnh , y ngun
nguyn liu sch, thn thin vi mi trng nn hon ton m bo chc nng thay th cho
phenol trong phn ng to keo. Trong phm vi ti ny, chng ti tin hnh nghin cu
nh hng ca cc yu t n phn ng tng hp keo polyphenols formaldehyde t
Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 7 i hc Nng nm 2010
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ngun polyphenols v keo l trm v th kh nng dn g ca keo sn phm.
2. Nguyn liu v phng php nghin cu
2.1. Nguyn liu
V cy keo l trm ra sch, thi nh bng dao kim loi khng r, sy 80
0
C v
xay thnh dng bt mn.
2.2. Phng php nghin cu
2.2.1. Xc nh mt s ch tiu ha l
Tin hnh xc nh m v hm lng tro trong mu bt nguyn liu kh.
2.2.2. nh tnh v nh lng polyphenol
Tin hnh nh tnh xc nh s c mt ca polyphenol trong dch chit ra v dng
phn ng Stiasny nh tnh phn bit polyphenol thuc nhm tanin ngng t v tanin thy
phn.
nh lng polyphenol thuc nhm tanin tch ra t mu nguyn liu ban u v t
mu polyphenol rn bng phng php Lowenthal [5].
2.2.3. Tch polyphenol rn v xc nh thnh phn cu to
Polyphenol rn c tch theo quy trnh c sn, em mu i chp ph IR v phn
tch sc k lng cao p ghp khi ph (HPLC- MS) xc nh thnh phn cu to.
2.2.4. Nghin cu ch s Stiasny ca polyphenol rn (1)
Tin hnh nghin cu Stiasny bng phn ng ca polyphenol rn vi HCHO trong
mi trng axit HCl.
2.2.5. Nghin cu nh hng cc yu t n phn ng tng hp keo polyphenol
formaldehyde
Nghin cu nh hng ca yu t t l khi lng polyphenol : th tch
formaldehyde v yu t thi gian n phn ng to keo polyphenol formaldehyde.
Tin hnh o nht ca dung dch keo thu c bng nht k canon Y683 xc
nh iu kin ti u.
2.2.6. Nghin cu tnh cht ca keo dn polyphenol formaldehyde
Tin hnh xc nh cc tnh cht ca keo: hm lng rn trong keo, pH, thi
gian gel ha, t trng v nht.
2.2.7. Nghin cu ng dng dn g ca keo polyphenol formaldehyde
Tin hnh dn g v kim tra bn mi dn.
3. Kt qu v tho lun
3.1. Xc nh mt s ch tiu ha l
Bng phng php bo ton khi lng ta tm c m mu nguyn liu kh l
11.06% v khong 14.90% hm lng tro.
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Hnh 3.1. Ph hng ngoi polyphenol
3.2. nh tnh v nh lng polyphenol
3.2.1. nh tnh polyphenol nhm tanin
Dch chit t v keo l trm cho phn ng dng tnh vi dung dch FeCl
3
5% (c
mu xanh en) nn trong dch chit c mt polyphenol nhm tanin.
Tin hnh phn ng Stiasny dch chit trong mi trng HCl, vi HCHO 37%, thy
xut hin kt ta vn mu ; dch lc trong sut chuyn mu xanh khi cho dung dch
CH
3
COONa d v dung dch FeCl
3
. Vy dch chit c polyphenol nhm tanin ngng t v
thy phn.
3.2.2. nh lng tanin trong mu nguyn liu ban u
un cch thu 2g bt nguyn liu trong 50ml nc ct un si khong 15 pht.
Tin hnh nh lng theo phng php Lowenthal cho hm lng tanin 11.20%. Hm
lng ny c chp nhn khi s dng ngun polyphenol v keo l trm.
3.2.3. nh lng polyphenol nhm tanin trong mu polyphenol rn
Cn 2g bt polyphenol rn, ha tan vo nc nng, lc v nh mc ln 250ml.
Tin hnh nh lng bng phng php Lowenthal cho kt qu 73.19%. iu ny chng
t hm lng tanin trong mu polyphenol l kh cao, thun li cho phn ng to keo dn.
3.3. Tch polyphenol rn v xc nh thnh phn cu to
3.3.1. Tch polyphenol rn
Polyphenol c tch theo quy trnh c sn, sau dng clorofom loi tp cht
trong dch chit. Tip tc em x l dch chit bng dung mi etylaxetat th polyphenol
chuyn vo tng etylaxetat. Ct loi etylaxetat ta thu c polyphenol rn.
3.3.2. Phn tch tanin bng ph hng ngoi IR


Bng 3.1. Tn s v loi dao ng trong ph hng ngoi ca polyphenol
Tn s, cm
-1
Loi dao ng Tn s, cm
-1
Loi dao ng
3400
1619
1447
-OH(ht)
C=O (ht)
C = C thm (ht)
1206
1045
1352
C- O (ht)
C- O (ht)
C = C thm (ht)
Vy polyphenol rn trong v cy keo l trm c cc nhm chc ph hp vi cng
thc cng b.
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3.3.3. Phn tch sc k lng cao p ghp khi ph (HPLC- MS)

Bng 3.2. Cc i lng c trng ca mt s cu t trn sc k HPLC
ca tanin tch t v keo l trm

Qua bng 3.2 ta thy c 16 cu t c tch ra v tip tc em phn tch bng ph
khi

Cn c vo kt qu trnh by bng 3.2 v da vo hnh 3.3, 3.4, 3.5, 3.6 chng ti
xut cc hp cht polyphenol c trong mu rn
Hnh 3.3: Cu t ca polyphenol- 1, khi lng ca [M+H]
+
= 202, M = 201.
Hnh 3.2: sc k HPLC ca tanin c tch t v keo l trm

Hnh 3.3: Ph khi lng ca cu t polyphenol- 1
Hnh 3.6: Ph khi lng ca cu t polyphenol- 14
Hnh 3.4: Ph khi lng ca cu t polyphenol- 12
Hnh 3.5: Ph khi lng ca cu t polyphenol- 9
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Cng thc phn t: C
9
H
13
O
5

Phn t khi: 201
Hm lng % trong sn phm polyphenol rn: 12,078%
Cng thc cu to:
OH
O
OH
OH
HO

Hnh 3.4: cu t ca polyphenol - 12, khi lng phn t ca [M+2H]
+
= 340, M = 338.
Cng thc phn t: C
14
H
10
O
10

Phn t khi: 338
Tn gi: hexa hydro xydiphenic acid (HHDP)
Hm lng % trong sn phm polyphenol rn: 11,5711%
Cng thc cu to:
HO
HO OH HO OH
OH
COOH COOH

Hnh 3.5: polyphenol - 9, khi lng phn t ca [M+ H]
+
= 301
Cng thc phn t: C
14
H
6
O
8
Phn t khi: 302
Tn gi: ellagic acid
Hm lng % trong sn phm polyphenol rn: 19,3521%
Cng thc cu to:
HO
HO O OH
OH
O
O
O

Hnh 3.6: polyphenol - 14, khi lng phn t ca [M+ H]
+
= 284
Cng thc phn t: C
15
H
11
O
6
Phn t khi: 287
Tn gi: Luteolinidin
Hm lng % trong sn phm polyphenol rn: 8,7683%
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Cng thc cu to:
OH
O
OH
HO
OH
OH

3.4. Nghin cu ch s Siasny ca polyphenol rn
Dch chit t 2g bt kh, 10ml dung mi nc trong 1h 90
0
C c lc v nh
mc ln 500 ml. Tin hnh phn ng stiasny 100ml dch + 10ml HCHO 37% v 5ml HCl
c trong thi gian 30 pht, 90
0
C, thu m
1
(g) kt ta. Song song tin hnh ui dung mi
cng lng dch chit 60
0
C, thu c m
2
(g) cht rn. Ta c kt qu ch s l 69.05
3.5. Nghin cu nh hng cc yu t n phn ng tng hp keo polyphenols
formaldehyde
3.5.1. nh hng ca t l khi lng polyphenol : th tch dung mi formaldehyde
Depolyme ha polyphenols 10g
polyphenols rn trong 100ml nc + 0.2g
Na
2
SO
3
90
0
C, ko di 90 pht nhm tng kh
nng phn ng [6]. Sau , tin hnh kho st
phn ng vi formaldehyde 100
0
C trong
khong 3h vi pH = 8 [2], vi cc t l khc
nhau. o nht dung dch keo chn iu
kin ti u.
Kt qu trn hnh 3.7 cho thy, t l khi lng polyphenols : th tch dung mi
formaldehyde ti u l 10g : 60 ml.
3.5.2. nh hng ca thi gian
Sau khi la chn c iu kin ti u
cho t l rn lng, ta dng t l rn lng ti u
tin hnh kho st yu t thi gian vi cc
khong thi gian khc nhau: 3h; 3,5h; 4h; 4,5h
v 5h 100
0
C, pH = 8. T hnh 3.8 c khong
thi gian 4h l tt nht.
3.6. Nghin cu tnh cht ca keo polyphenol formaldehyde
Tin hnh xc nh hm lng cht rn trong keo, thi gian gel ha [7], o pH
dung dch keo bng thit b Denver Instrument Basic, xc nh t trng bng bnh t trng
picnomet, v o nht k ta c cc thng s tnh cht:
Bng 3.3: kt qu cc tnh cht keo
Hm lng rn (%) Thi gian gel ha (s) pH T trng (g/cm
3
) nht (cPs)
40.685 120 5.9 1.272 3193.43
Hnh 3.8: nh hng ca thi gian
Hnh 3.7: nh hng ca t l rn : lng
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3.7. Nghin cu ng dng dn g ca keo polyphenol formaldehyde
3.7.1. Ph hng ngoi keo
T ph hng ngoi sn phm (hnh 3.6) ta thy c nhm OH(ht) ancol v = 3430.26
cm
-1
, nhm CH
2
(bd) vi v = 1381.92 cm
-1
chng t sn phm c nhm methylol -CH
2
OH
v c cu ni methylene ca keo.

3.7.2. ng dng dn g
Sn phm keo to thnh c axit ha bng axit oxalic v gia nhit 130
0
C, vi p
sut 7.5 kg/cm
2
trong thi gian 15 pht [6]. Sau em mu i xc nh mi dn.
4. Kt lun
Qua qu trnh nghin cu, cho php chng ti a ra mt s kt lun sau:
Vi hm lng tanin 11.20% trong v th v 73.19% trong mu polyphenol rn
tch ra, th v keo l trm l ngun nguyn liu kh thun li trong phn ng to
keo dn.
Lng tanin ngng t trong lng polyphenol tng tch ra bng dung mi etanol
tng i cao. Ta chn etanol lm dung mi tch polyohenol cho phn ng to
keo.
tm c iu kin ti u cho phn ng to keo polyphenol - formaldehyde l: t
l rn : lng = 10 gam : 60ml, thi gian 4h.
Keo sn phm c cc tnh cht ph hp vi tnh cht keo dn, v c kh nng dn g.

TI LIU THAM KHO

[1] S Sowunmi, RO Ebewele, O Peters and AH Conner (2000), Differential scanning
calorimetry of hydrolysed mangrove tannin, Polymer International, (49/2000), page
574 - 578.
[2] W. E. Hillis and Gerda Urbach (1959), Reaction of polyphenols with formaldehyde,
J. appl. Chem, 9, December, page 665 - 672.
[3] S. E. Drewers and D. G. Roux (1966), A New Flavan 3,4 diol from Acacia
auriculiformis by Paper Ionophoresis, Biochem. J, (98/1966), page 493 - 500.
[4] Nguyn Quc Tn, Phm L Dng, Keo dn, NXB khoa hc k thut, H Ni.
Hnh 3.9: ph hng ngoi keo polyphenol formaldehyde
Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 7 i hc Nng nm 2010
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[5] B Y t (1980), Bi ging dc liu tp 1, NXB Y hc, H Ni.
[6] Hunh i Ph, hng dn th nghim ha hc polyme,NXB HQG H Ch Minh.
[7] L. T. Chew, W. C. Wong, Mohd Sukari Midon (1988), A Study On The Properties
Of Synthetic Adhesive Available In Peninsular Malaysia, Journal of Tropical Forest
Science 3, page 196 203.