Starch Based Thickening agents for

Personal Care Surfactant Systems

B. Volkert, A. Lehmann, A. Schrader, H. Nerenz
58
th
Starch Convention, Detmold, April 25 27
Index of contents
1. Requirements and objectives
2. Approach of resolution
2.1 Carboxymethylation of starch (CMS)
2.2 Hydrophobic modification of CMS
2.3 Variation of the surfactant system
3. Summary
high viscosity by lowapplication concentration
long-termstability over a pH-range ~4 9
electrolyte und surfactant compatibility
high transparency of the gel
simple workability (quick swelling and pH-adjustment)
biological degradation
cheap
toxicological harmlessness
satisfy appliance properties (e.g. no gluey feeling on the skin)
Profile of qualification of a modern thickening agent for
surfactant systems
1. Requirements and objectives
Used surfactant systems
14% Surfactant 2% Chemical modified starch
O
O C
12
SO
3
Na
n
n =12-14
2.) Anionic Surfactant ! Sodiumlaurethsulfate (SLES)
" less kindness to the skin as APG
" easier to thicken
O
HO
HO
OH
OH
O
O
HO
HO
OH
O
(CH
2
)
n
m
m = 0-3; n = 12 - 16
1.) Nonionic surfactant !Alkyl polyglucoside (APG)
" high kindness to the skin
" not easy to thicken
" synergistic effect with anionic surfactants
1. Requirements and objectives
" Synthesis of a starch based thickener for personal surfactant systems
" high transparency
" formulations should obtain a customary viscosity (~ 6000 mPas)
Objectives for this project
1. Requirements and objectives
1
st
Approach of resolution
Use of Carboxymethyl starch as thickening agent
2.1 Carboxymethylation of starch
O
O
HO
O
OH
HO
O
HO
O
OH
HO
O
HO
O
OH
HO
O
O
HO
O
OH
O
O
HO
O
OH
HO
O
HO
O
O
HO
NaOH; i-PrOH;
40C; 4.5h
CO
2
-
Na
+
CO
2
-
Na
+
Cl-CH
2
-COOH
1565
20685
2260
5680
8140
17870
0
5000
10000
15000
20000
25000
0.55 1.08 1.45
Degr ee of subst i t ut i on
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5
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-
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0% Surfactant
14% APG
Shear viscosity of 2% CMS-solutions
" CMS obtain a thickening effect for
APG
" CMS with a DS~1 shows
maximumshear viscosity
2.1 Carboxymethylation of starch
86.5
82.0
67.0
5.0
2.5
6.5
0
20
40
60
80
100
0.55 1.08 1.45
Degr ee of subst i t ut i on
T
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[
%
]
0% Surfactant
14% APG
" only solutions of CMS without APG
are bright
" solutions of CMS with APG are
milky white with lowtransparency
Transparency of 2% CMS-solutions
2.1 Carboxymethylation of starch
2
nd
Approach of resolution
Use of hydrophobic carboxymethyl starch as thickening agent
2.2 Hydrophobic modification of Carboxymethyl starch
Hydrophobic substitution of carboxymethyl starch
Etherfication Esterfication
e.g. Reaction with
1,2-Epoxyalkanes
Alkyl halogenides
e.g. Reaction with
Acid halogenides
2.2 Hydrophobic modification of carboxymethyl starch
Starch
Alkylation (hom.) Carboxymethylation (het.)
Carboxymethylation (het.) Alkylation (het.)
Hydrophobation: Reaction with 1,2-Epoxyalkanes
Hydrophilation: Reaction with Monochloroacetic acid
1. Hydrophobation 1. Hydrophiliation
2. Hydrophilation
2. Hydrophobation
Possibilities for synthesis
2.2 Hydrophobic modification of carboxymethyl starch
O
O
HO
O
OH
HO
O
HO
O
OH
HO
O
HO
O
OH
HO
O
O
HO
O
OH
O
O
HO
O
OH
HO
O
HO
O
O
HO
140C; 4h; 3bar
CH
3
O
n
n =5, 7, 9
Base
n
n
CH
3
H
3
C
HO
OH
2 Reaction channels
Bien et al. NaOH (0.5 eq); Na
2
SO
4
(0.5 eq); Epoxyalkanes (1.2 eq)
Funke et al. KOH (0.8 eq); Epoxyoctane (1.0 eq)
Homogeneous Hydrophobation
2.2 Hydrophobic modification of carboxymethyl starch
Homogeneous Hydrophobation
2.2 Hydrophobic modification of carboxymethyl starch
C
6
! 2-Hydroxyhexyl starch DS = 0.8
C
8
! 2-Hydroxyoctyl starch DS = 0.7
C
10
! 2-Hydroxydecyl starch DS = 0.9
C
12
! 2-Hydroxydodecyl starch DS = 0.9
O
O
HO
O
OH
HO
O
HO
O
OH
HO
O
HO
O
OH
HO
O
O
HO
O
OH
O
O
HO
O
OH
HO
O
HO
O
O
HO
140C; 4h; 3bar
CH
3
O
n
n = 5, 7, 9
Base
n
n
CH
3
H
3
C
HO
OH
"starch isnt complete decomposed
"remaining starch chains can react with
1,2-epoxyalkanes
10
3
10
4
10
5
10
6
10
7
10
8
0,0
0,2
0,4
0,6
0,8
1,0
1,2


d
W
/
d
(
l
o
g

M
)
Molar mass [g/mol]
M
w
[10
6
g/mol]
wms after reaction 6.4
waxy maize starch 54.0
Molar mass distribution of waxy maize starch
2.2 Hydrophobic modification of carboxymethyl starch
O
O
HO
O
OH
O
O
HO
O
OH
HO
O
HO
O
O
HO
NaOH; i-PrOH;
40C; 4h
CH
3
O
O
HO
O
OH
O
O
O
O
OH
HO
O
HO
O
O
O
CO
2
-
Na
+
+
Na
-
O
2
C
H
3
C
HO
n
H
3
C
HO
OH
CH
3
OH
Cl-CH
2
-COOH
n
n
n
1. Carboxymethylation of 2-Hydroxyoctylstarch with 1-3 eq MCE
2. Studies of these starch derivatives in surfactant system
3. Using the best results to synthesise C
6
, C
10
and C
12
hydrophobic starches
Heterogeneous Hydrophilation
2.2 Hydrophobic modification of carboxymethyl starch
7540
6910
6165
55 80 30 15
5055
0
2000
4000
6000
8000
C6-CMS C8-CMS C10-CMS C12-CMS
st ar ch der i vat i ve
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0 % Surfactant
14% APG
SD DS
2-Hydroxyalkyl
DS
Carboxymethyl
C
6
-CMS 0.8 0.83
C
8
-CMS 0.7 0.92
C
10
-CMS 0.9 0.84
C
12
-CMS 0.9 0.65
(C
6
=2-Hydroxyhexyl-; C
8
=2-Hydroxyoctyl-;
C
10
=2-Hydroxydecyl-; C
12
=2-Hydroxydodecyl)
Shear viscosity of 0.5% 2-Hydroxyalkylcarboxymethyl starch solutions
2.2 Hydrophobic modification of carboxymethyl starch
95
95
92
54
21
60
68
74
0
20
40
60
80
100
C6-CMS C8-CMS C10-CMS C12-CMS
st ar ch der i vat i ve
T
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[
%
]
0 % Surfactant
14% APG
SD DS
2-Hydroxyalkyl
DS
Carboxymethyl
C
6
-CMS 0.8 0.83
C
8
-CMS 0.7 0.92
C
10
-CMS 0.9 0.84
C
12
-CMS 0.9 0.65
(C
6
=2-Hydroxyhexyl-; C
8
=2-Hydroxyoctyl-;
C
10
=2-Hydroxydecyl-; C
12
=2-Hydroxydodecyl)
Transparency of 0.5% 2-Hydroxyalkylcarboxymethyl starch
solutions
2.2 Hydrophobic modification of carboxymethyl starch
Analysis by static light scattering (SLS)
0
1x10
10
2x10
10
3x10
10
4x10
10
5x10
10
6x10
10
7x10
10
-19,0
-18,5
-18,0
-17,5
-17,0

l
n
(
K
*
c
/
R
(
!
)
)
q
2
2-Hydroxyoctylcarboxymethyl starch
Carboxymethyl starch
Alkylpoly glucoside
Dilutuion 1:10
2.2 Hydrophobic modification of carboxymethyl starch
2-Hydroxyoctyl-CMS
DS
CM
= 0.9
DS
2-HO
=0.7
Carboxymethyl starch
DS
CM
= 1.1
CMS C
8
/CMS C
10
/CMS C
12
/CMS
2.2 Hydrophobic modification of carboxymethyl starch
APG solutions with different hydrophobic modified CMS
2.3 Variation of the surfactant system
3
rd
Approach of resolution
Use of surfactant mixture APG/SLES
8160
29710
2830
35900
5165
98
70
91
95
65
0
5000
10000
15000
20000
25000
30000
35000
40000
2-HDOCMS
14% APG
0% SLES
2-HDOCMS
14% APG
1% SLES
2-HDOCMS
14% APG
2% SLES
2-HDOCMS
14% APG
3% SLES
2-HDOCMS
14% APG
5% SLES
sur f act ant mi xt ur es
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50
55
60
65
70
75
80
85
90
95
100
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[
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" by adding SLES viscosity
and transparency of the
formulations increase
" max. of viscosity and trans-
parency by adding 3% SLES
" addition of >3 % SLES
viscosity and transparency
decrease
Shear viscosity and transparency of different surfactant
mixtures
2.3 Variation of the surfactant system
1% 2-HDOCMS
14% Alkylpoly glucoside
1% 2-HDOCMS
14% Alkylpoly glucoside
1% SLES
"(#=2.55 s
-1
) = 5165 mPas
T = 70 %
"$#%2.55 s
-1
) = 8160 mPas
T = 91 %
Comparison of formulations with and without
SLES
2.3 Variation of the surfactant system
3. Summary
" selective aqueous surfactant systems can be stable thicken by
modified CMS (~0,5% concentration)
" viscosity and transparency can be controlled bv varying the DS
hydrophobic-hydrophilic and addition of SLES
" in principle application as emulsifying agent for O/W-emulsionens
possible
Thanks to
" Dr. Waltraud Vorwerg for the GPC and SLS data
" Dr. J rgen Kunze for recording the
13
C-NMR data
" Inst. Dr. Schrader for the cooperation
" Agency for renewable resources for the financial support