Synthesis and Properties of Hydrophobic Starches

Transcription

1 Synthesis and Properties of Hydrophobic Starches Waltraud Vorwerg, Kay Hettrich, Sylvia Radosta 59. Starch Convention; Detmold, April 16-17, 2008

2 utline Introduction Synthesis of starch esters -Alkenylsuccinate starch -Ester with fatty acid chlorid Synthesis of starch ethers -Benzylated starch -Epoxidised triglycerides -Glycidic ethers bi- and trifunctional Amphiphilic starch Investigation of application Summary 59. Starch Convention; Detmold, April 16-17,

3 Introduction Potentially technical applications of starch derivatives require improved resistance to diffusion and penetration of water. Desire Stability against high humidity of air and penetration of water The general concept of water resistant starch are classified according the application areas or properties: Modified Starch is utilised to improve the sensitivity of textile fibre against wetness by reinforcement of bonds between fibres Modified Starch is applied as water-repellent (hydrophobic) agent reducing penetration of moisture Application fields: Surface sizing in paper making, adhesive for paper and corrugated board, textile sizing and finishing 59. Starch Convention; Detmold, April 16-17,

4 Synthesis of esters Alkenyl succinate starch Starch + T, Solvent catalyst - H 2 SA Succinic acid derivatives: H HC SA: ctenyl- DDSA: Dodecenyl- LASAR: Alkenyl- (C 16 -C 18 ) H H H H H H H H H ctenyl succinate starch 59. Starch Convention; Detmold, April 16-17,

5 Synthesis of esters Alkenyl succinate starch reagent yield between 50 und 90% reaction efficiency is increasing according the following conditions: - efficiency of reagent: SA >> DDSA > ASA - homogeneous state of swelling of the starch during reaction - high ratio of starch : water - NaH is more suitable than Na 2 C 3 - reaction temperature between C molecular degradation is limited at ph Starch Convention; Detmold, April 16-17,

6 Ester with long alkyl chains Fatty acid chlorides: - ctanoyl chlorid - Polymergin acid chloride DS: 0,06...0,15 St arch M NaH 2. Cl H H - H 2, - Na +, - Cl - H H H H H H H H Advantage: - quick reaction Disadvantages: - hydrolysis of reagent - unavailability of commercial chlorides of fatty acids 59. Starch Convention; Detmold, April 16-17,

7 Ester with ctanoyl and Polymergin acid Dynamic rheology Molar mass distribution d.s. M W [10 6 g/mol] HS-15 0, HS-21 0, HS-34 0, G', G'' [Pa] HS-21 G' HS-21 G'' HS-34 G' HS-34 G'' dw/d(log M) measuring temp. 60 C Frequency [Hz] Molar mass [g/mol] 59. Starch Convention; Detmold, April 16-17,

8 Synthesis of ethers benzyl starch Principle: Benzylation (DS 0,1... 0,25) Change of distribution of particle size by pressure cooking H CH 2 H H H H H H H + - HCl Cl H CH 2 H H H H H H Volume (%) Jet-coker native potato starch hydrophobic dispersion Particle size (µm) Dispersion with stable viscosity Sedimentation 59. Starch Convention; Detmold, April 16-17,

9 Ethers with epoxidised triglycerides C C C H H R C C C H H 2 C C H H C C H H C C H H 2 C R R + Starch + H - Bien et al Autoklave - Temperature: 120 bis 160 C -NaH, H 2, Na 2 S 4 H R' H H H H H H H H H 59. Starch Convention; Detmold, April 16-17,

10 Ethers of triglycerides with linseed and soy been oil Composition Components: linseed oil soy been oil linolenic acid 52% 8% linoleic acid 17% 56% oleic acid 22% 21% stearic acid 4% 4% palmitic acid 5% 10% Lein: Edenol B 316 (Fa. Cognis), EL (Fa. Hobum) Soja: Edenol D81 (Cognis), ESB u. EME (Hobum) 59. Starch Convention; Detmold, April 16-17,

11 Molecular composition of ethers with triglycerides Kind of oil DS M w [10 6 g/mol] Soy (HS-14) 0,06 2,64 Soy (HS-20) 0,03 3,61 Soy (HS-25) * 0,01 2,38 dw/d(log M) 0,9 0,8 0,7 0,6 0,5 0,4 0,3 M W [10 6 g/mol] HS HS HS HS HS HS Soy (HS-30) 0,03 3,16 0,2 0,1 Lin (HS-17) 0,05 8,92 Lin (HS-23) 0,02 8,68 *methyl ester 0, Molar mass [g/mol] different molecular degradation by applied synthesis conditions 59. Starch Convention; Detmold, April 16-17,

12 Flow behaviour of ethers with triglycerides Viscosity [Pa s] measuring temperature: 60 C HS-14 HS-17 HS-20 HS-23 HS-25 HS-30 Viscosity is not dependent on kind of epoxidised triglyceride but more on the degree of substitution, synthesis conditions respectively swelling state in aqueous solution Shear rate [1/s] 59. Starch Convention; Detmold, April 16-17,

13 Synthesis with glycidic ethers - bifunctional GE11: Cyclohexandimethanol-diglycidic ether GE14: Neopentylglycol-diglycidic ether CH 3 CH 3 GE19: Polypropylenglycol-diglycidether CH 3 n, n= Starch Convention; Detmold, April 16-17,

14 Synthesis with glycidic ethers - bifunctional Flow behaviour Stress sweep Viscosity [Pa s] measuring temperature 80 C Corn starch GE11 GE14 GE19 G', G'' [Pa] measuring temperatre 20 C Corn starch G' Corn starch G'' GE11 G' GE11 G'' GE14 G' GE14 G'' GE19 G' GE19 G'' Shear rate [1/s] Shear stress [Pa] 59. Starch Convention; Detmold, April 16-17, 2008

15 Synthesis with glycidic ethers - trifunctional GE9: Polyglycerol-triglycidic ether GE12: Glycerin-triglycidic ether n, n= Starch Convention; Detmold, April 16-17,

16 Synthesis with glycidic ethers - trifunctional Flow behaviour Stress sweep 10-1 measuring temperature 80 C Viscosity [Pa s] Maisst aerke GE12 GE9 G', G'' [Pa] Corn starch G' Corn starch G' ' GE12 G' GE12 G'' GE09 G' GE09 G'' 4x10 0 6x10 0 8x Shear rate [1/s] shear stress [Pa] 59. Starch Convention; Detmold, April 16-17, 2008

17 Amphiphilic starch with hydrophobic Quab Cl - N + CH 3 R CH 3 + H - - H 2, - Cl - Cl R Cl - CH 3 H N + CH 3 R: Dodecyl- (Quab 342), Cocoalkyl- (Quab 360), Stearyl- (Quab 426) Quab + Starch (H - ) Amphiphilic starch H H H 3 C R H H H N + CH 3 H H H H H H Müller, Gruber et al Starch Convention; Detmold, April 16-17,

18 Amphiphilic starch with hydrophobic Quab Heterogeneous or homogeneous reaction in dependence on the type of material Reaction temperature 40 bis 80 advantage: short time of reaction disadvantage : surfactant properties of reagents Potential of application: Paper additiv, adhesive und textil sizing replacement of polyacrylate 59. Starch Convention; Detmold, April 16-17,

19 Amphiphilic starch with hydrophobic Quab Molar mass distribution Frequency sweep M W [10 6 g/mol] Quab Quab Quab dw/d(log M) Molar mass [g/mol] G', G'' [Pa] measuring temperature 60 C frequency [Hz] Quab342 G' Quab342 G'' Quab360 G' Quab360 G'' Quab426 G' Quab426 G'' 59. Starch Convention; Detmold, April 16-17,

20 Surface sizing of paper Investigation of application Application of aqueous starch dispersion with size press before sizing Defined method for water adsorption Cobb 60 test Inkjet-printability ink density, ink penetration after sizing Contact angle 59. Starch Convention; Detmold, April 16-17,

21 Hydrophobic starch - Cobb 60 -Value Cobb 60 -Value Degree of substitution SA 0,07 Quab 342 0,03 Quab 360 0,02 Quab 426 0,02 ctanoyl 0,07 10 Polymergin acid 0,06 0 SA Quab 342 Quab 360 Quab 426 ctanoyl Polymerg. Epoxylipid Starch derivative Epoxy triglyceride 0,02 Dr. K.L. Woll, Emsland-Stärke GmbH 59. Starch Convention; Detmold, April 16-17,

22 Investigation of water penetration Determination of the velocity of water penetration Starch on copper sheet needle droplet of water ca. 20 µl needle touches the surface of the film film copper sheet water droplet Ω Measurement of resistance between copper Ω sheet and pin in dependence on time resistance is high at the start and breaks down when the drop of water has penetrated the film. St. Kröpke, A. Holländer (IAP) Advantage: quick and easy method with small portions of the film sample. 59. Starch Convention; Detmold, April 16-17,

23 Hydrophobic Starch - water penetration SA Starch Different hydrophobic starches Voltage, V 0,1 0,0-0,1-0,2-0,3-0,4 Time [s] Thickness of the film layer 100µm Epoxi Lasar SA SA SA Epoxi Epoxi Epoxi Quab Epoxi Epoxi ctanoyl -0,5-0,6-0,7 d, µm t, s SA (1. measurem.) SA (2. measurem.) SA (3. measurem.) calculated curve 1. Determination of time Time, s Starch Convention; Detmold, April 16-17,

24 Hydrophobic starch inkjet printing Density D = -log b b = Reflexion 100 % 100 % 100 % 100 % 10 % 1 % b = 1,0 b = 0,1 b = 0,01 D = 0 D = 1,0 D = 2,0 Papier b = reflected light/emitted light D = log 1/b Dr. K.L. Woll, Emsland-Stärke GmbH 59. Starch Convention; Detmold, April 16-17,

25 Effects of hydrophobic starches in surface sizing Kind of derivative D.S. Cobb 60 -Value Colour density SA 0, ,7 Quab 342 0, ,5 Quab 360 0, ,3 Quab 426 0, ,4 ctanoyl 0, ,6 Polymergin 0, ,1 Epoxy tryglyceride 0, ,5 Dr. K.L. Woll, Emsland-Stärke GmbH 59. Starch Convention; Detmold, April 16-17,

26 Hydrophobic starch - conclusions Hydrophobic reagents with different chemical structure are suitable for the modification of starch influencing surface properties of paper. Reaction efficiency is dependent on the kind of reagent; e.g. anhydride or epoxid, length of alkylene chains and the presence of phenyl groups. ptimized reaction conditions cause only low molecular degradation of the starch and guarantee film forming properties. The degree of substitution ( ) is dependent on starch type or derivative. The hydrophobization of starch can be combined with ionic ethers to develop amphiphilic starch products. 59. Starch Convention; Detmold, April 16-17,

27 Acknowlegement Financial support: Agency for Renewable Recources/ BMELV Co-workers of IAP Dr. Kay Hettrich Dr. Sylvia Radosta Dr. Andreas Ebert Matthias Nenneker Stefan Kröpke Stephan Lang Gabriela Reimer Marion Stage Barbara Brettnacher Dr. Andreas Holländer Industry partner: Emsland-Stärke GmbH, Hobum Fettchemie, UPPC AG 59. Starch Convention; Detmold, April 16-17,

28 Contact address: Dr. Waltraud Vorwerg Wissenschaftspark Golm Geiselbergstraße Potsdam-Golm phone: +49/ Starch Convention; Detmold, April 16-17,