SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
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SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS Martin Häubl (ESIM Chemicals GmbH) C. Pretschuh, M. Steiner. M. Mihalic (Wood K Plus, Linz, Austria) Chemspec 2018
ESIM CHEMICALS AT A GLANCE
ESIM Chemicals is a global leader in
custom development and production
of fine chemicals for various industries
and a flexible supplier of maleic
anhydride, fumaric acid, maleates, 520 75+
succinates and fumarates. Employees Years of Expertise
200 2
MEUR Net Sales Business Clusters
ESIM Chemicals 2
CHEMISTRY PARK LINZ AT A GLANCE
Linz is the home of a well established
and globally active chemical industry. >40 3,500
Companies Employees
1.2 km2 31 km
Area Railway net
2,500 300
MEUR MEUR
Replacement Value Infrastructure
ESIM Chemicals 3
MARKETS WE FOCUS ON
Crop Protection Polymers
Pharma Food Feed
Electronics Cosmetics
Personal Care
ESIM Chemicals 4
BUSINESS CLUSTERS
Exclusive Synthesis Intermediates
ESIM Chemicals 5
EXCLUSIVE SYNTHESIS
CORE TECHNOLOGIES OF ESIM INCLUDE:
Continuous Hydrogenation
Processing
Melt Advanced Esterification
and Liquid Catalysis
Handling
Distillation Solid Material
Handling
ESIM Chemicals 6
A HUGE VARIETY OF PLATFORM CHEMICALS AND SPECIALTIES ESIM Chemicals 7
HIGH QUALITY STANDARDS ESIM Chemicals 8
WHEN HAVE YOU USED A HYDROGEL FOR
THE LAST TIME?
Ref. to: https://www.ratgeber-hautgesundheit.de/pflege/kosmetik/
Ref. to: http://wienerin.at/home/leben/gesundheit/5217921/
ESIM Chemicals 9
WHAT IS A HYDROGEL?
Dry solid (collapsed) Hydrogel (swollen network)
Water
Polymer Chain
Crosslinker
ESIM Chemicals 10MAJOR APPLICATIONS FOR HYDROGELS /
MARKET PERSPECTIVE
Cosmetic products
Soft contact lenses
Hygiene products (Superabsorbent fillers in diapers)
Ref. to: https://www.theeyegalleryok.com/
Wound dressings
Tissue engineering scaffolds
Drug delivery
Agriculture (water conservation) Ref. to: https://www.alibaba.com/
Food products
Strong future market growth (CAGR 8%) in all
applications
Ref. to: http://www.marineagar.net/
ESIM Chemicals 11WHY ARE HYDROGELS WIDELY USED IN
COSMETICS?
To improve sensory properties of a lotion or cream
Thickening agent
Control release of active ingredients
Ref. to: https://receptranaturals.com/
Bio-compatibility
High water content
Elasticity and softness
Naturally sources (protein chains, polysaccharides)
Ref. to: https://www.dreamstime.com/
Ref. to: https://www.nationalgeographic.org/
ESIM Chemicals 12HOW TO IMPROVE HYDROGELS?
Polymer
Make use of naturally derived and sustainable materials
(Polysaccharides, etc.) to substitute crude oil based polyacrylates
Crosslinker
Use a highly efficient crosslinker which leads to high performance
hydrogels (swelling, rheological behavior)
Substitute crosslinkers like epichlorohydrin, divinylsulfone, and
various anhydrides by harmless materials, which are not
cancerogenic to reduce toxic residues within the hydrogel
Use of crosslinkers, which are readily biodegradable
ESIM Chemicals 13NATURALLY DERIVED POLYMERS:
CELLULOSIC DERIVATIVES
Carboxymethylcellulose Sodium (CMCNa)
Low cost naturally derived polysaccharide
Biocompatible and biodegradable
High molecular weights and low degree of substitution increases
crosslinking ratio [1],[2]
Hydroxyethylcellulose (HEC)
Biocompatible and biodegradable
Spacer material to improve swelling of crosslinked hydrogels
As it is less sterically hindered than CMCNa crosslinking is
promoted using this material [2]
[1] Ref. to: J. Appl. Polym. Sci. 110, 2453-2460, 2008
[2] Ref. to: Carbohydrate Polymers 137, 2016, 59-64
ESIM Chemicals 14SULFOSUCCINIC ACID AS CROSSLINKER:
BIODEGRADABLE AND NON-TOXIC
Sulfosuccinic esters are already well-known in the O O
cosmetic ingredient sector (e.g. DOSS) HO
S
OH
O
Excellent biodegradability OH
Excellent thermal crosslinker for hydrophilic naturally O
derived polymers (e.g. polysaccharides)
Multifunctional: Crosslinking agent as well as
esterification catalyst
The insertion of a sulfonic acid group to the polymer
network improves its hydrophilicity which leads to
better swelling performance
Non-cancerogenic (in contrast to epichlorohydrin etc.)
ESIM Chemicals 15RAW MATERIALS FOR GEL PREPARATION
Polymers:
Carboxymethylcellulose Sodium (CMCNa)
Degree of substitution: 0.9
Mw: ~ 250.000
Na+: 8 wt%
Hydroxyethylcellulose (HEC)
Degree of substitution: 0.4
Mw: ~ 90.000
Crosslinker:
Sulfosuccinic Acid 99 %
Diluted to a 7 wt% aqueous solution
ESIM Chemicals 16PRINCIPLE OF CHEMICAL CROSSLINKING Ref. to: N. Reddy, R. Reddy, Qiuran Jiang, Trends in Biotechnology 33,6, p 362 – 369, 2015 ESIM Chemicals 17
CROSSLINKING REACTION USING
SULFOSUCCINIC ACID
Crosslinking of HEC and CMCNa with Sulfosuccinic Acid
OR OR
O O
RO O
O O R
RO RO
RO n
O
∆ O
O O
S
O O OH
HO O O
S OR'
OH
O O
OH O
R'O O
O R'O O R'
R'O R'O
R'O m
x H2 O
ESIM Chemicals 18SWELLING RATIOS OF CMCNa-HEC
HYDROGELS
CMCNa/HEC 3:1 gels crosslinked with
10 wt% Sulfosuccinic Acid (SSA) at different reaction times
Reaction: 60°C, Curing: 2 hours at 80°C
140
120
Swelling Ratio SR [%]
128
100
117
80
60
67
40
20
0
2 4 6
Reaction time [hours]
ESIM Chemicals 19VISCOSITY INCREASE DUE TO HIGHER
CROSSLINKING RATIO
CMCNa/HEC gels crosslinked with different amounts of
Sulfosuccinic Acid (SSA),
Reaction: 4 hours at 60°C, Curing: 2 hour at 80°C
CMCNa/HEC 3:1 with 3 % solid content,
parallel-plate-rheometer, 30°C, 1 – 10 % deformation
10000
Viscosity |η*| [Pa s]
1000
100
10
1
0,01 0,1 1 10 100
Angular Frequency w [rad/s]
0 % SSA 0.5% SSA 4% SSA 10% SSA
ESIM Chemicals 20PREPARATION OF CELLULOSE BASED
HYDROGEL USING SULFOSUCCINIC ACID
OPTIMIZED REACTION PARAMETERS
3:1 mixture of CMCNa/HEC in water (1.5 wt% total solid content)
Addition of Sulfosuccinic Acid as 7 wt% aqueous solution at 60°C
(10 wt% based on total amount of cellulosic derivatives)
Stirring of the reaction mixture at 60°C or 4 hours
Final curing and drying at 80°C for 2 hours
Swelling of the dried hydrogel in water to obtain a hydrogel with
5 wt% solid content
ESIM Chemicals 21VISCOSITY OF THE HYDROGEL AT
OPTIMIZED REACTION CONDITIONS
CMCNa/HEC 3:1 gel crosslinked with 10 wt% Sulfosuccinic Acid
(SSA), Reaction: 4 hours at 60 °C; Curing: 2 hours at 80°C
CMCNa/HEC 3:1 with 5 % solid content,
parallel-plate-rheometer, 30°C, 1 – 10 % deformation
10000
Viscosity |η∗| [Pa s]
1000
100
10
1
0,01 0,1 1 10 100
Angular Frequency ω [rad/s]
ESIM Chemicals 22COMPARISON WITH CARBOPOLS:
VISCOSITY
Parallel-plate-rheometer, 30°C, 1 – 10 % deformation
100.000
10.000
Viscosity |η∗| [Pa s]
1.000
100
10
1
0
0,01 0,1 1 10 100
Angular Frequency ω [rad/s]
Carbopol 980 3 wt% Carbopol 981 3 wt% CMCNa - HEC opt 5 wt%
ESIM Chemicals 23COMPARISON WITH CARBOPOLS:
REVERSIBLE ELASTIC LIMIT
Parallel-plate-rheometer, 30°C
100.000
10.000
Deformation γ [%]
1.000
100
10
1
0
1 10 100
Shear Stress τ [Pa]
Carbopol 980 3 wt% Carbopol 981 3 wt% CMCNa - HEC opt 5 wt%
ESIM Chemicals 24REM PICTURES OR FREEZE DRIED
HYDROGELS
CMCNa – HEC Gel opt (5 wt%) Carbopol 980 (3 wt%)
ESIM Chemicals 25CONCLUSIONS
Successful crosslinking of a biodegradable hydrogel without toxic
residues based on cellulose derivatives (CMCNa and HEC) using
Sulfosuccinic Acid.
Optimal crosslinking parameters were reached at a Sulfosuccinic Acid
level of 10 wt%, and crosslinking temperatures of 60°C for 4 hours
followed be a further curing step at 80°C for 2 hours. The obtained
hydrogel showed similar properties to commercially available Carbopol
(Polyacrylic Acid) gels.
A 5 wt% aqueous crosslinked cellulosic CMCNa-HEC Hydrogel showed
a rheological behavior similar to a 3 wt% aqueous Carbopol gel.
If the amount of Sulfosuccinic Acid exceeds 10 wt% the increased
crosslinking ratio results in a poor swelling behavior of the gel (limited
water accessibility to the polymer network).
ESIM Chemicals 26ACKNOWLEDGEMENT This study was performed together with the Competence Centre for Wood and Wood-related renewable resources (Wood K plus) and co- financed by the Austrian Research Agency FFG. ESIM Chemicals 27
CONNECT WITH US @ BOOTH F10
Dr. Martin Häubl
ESIM Chemicals GmbH
St.-Peter-Strasse 25
4020 Linz
Austria
Tel: +43 732 6982-2483
Mobile: +43 664 88236163
martin.haeubl@esim-chemicals.com
www.esim-chemicals.com
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