SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe

 
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
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
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
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
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
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
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
MARKETS WE FOCUS ON

   Crop Protection      Polymers

   Pharma        Food          Feed

   Electronics          Cosmetics
                        Personal Care

ESIM Chemicals                          4
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
BUSINESS CLUSTERS

                 Exclusive Synthesis   Intermediates

ESIM Chemicals                                         5
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
EXCLUSIVE SYNTHESIS
CORE TECHNOLOGIES OF ESIM INCLUDE:

   Continuous           Hydrogenation
   Processing

   Melt           Advanced     Esterification
   and Liquid     Catalysis
   Handling

   Distillation         Solid Material
                        Handling

ESIM Chemicals                                  6
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
A HUGE VARIETY OF PLATFORM CHEMICALS
AND SPECIALTIES

ESIM Chemicals                     7
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
HIGH QUALITY STANDARDS

ESIM Chemicals           8
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
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
SULFOSUCCINIC ACID: AN EFFICIENT CROSSLINKING INTERMEDIATE FOR COSMETIC HYDROGELS - Chemspec Europe
WHAT IS A HYDROGEL?

     Dry solid (collapsed)   Hydrogel (swollen network)

                                       Water

                                       Polymer Chain

                                       Crosslinker
ESIM Chemicals                                            10
MAJOR 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                                                                                   11
WHY 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                                                                                 12
HOW 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                                                               13
NATURALLY 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                                                                 14
SULFOSUCCINIC 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                                                               15
RAW 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                                    16
PRINCIPLE 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                                                                                                      18
SWELLING 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                                                                                    19
VISCOSITY 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                                                                                       20
PREPARATION 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                                                          21
VISCOSITY 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                                                                                       22
COMPARISON 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                                                                                            23
COMPARISON 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                                                                                   24
REM PICTURES OR FREEZE DRIED
HYDROGELS
     CMCNa – HEC Gel opt (5 wt%)   Carbopol 980 (3 wt%)

ESIM Chemicals                                            25
CONCLUSIONS
    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                                                               26
ACKNOWLEDGEMENT

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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