Alkyl polyglycosides(APG) 유도체인 APG Butyryl esters 합성과 물성

명진승, 오성근

한양대학교 화학공학과

The synthesis of alkyl polyglycoside butyryl  esters as derivative of                 APG and their properties, application

Myeoung jin seoung , Seong Geun Oh

Department of Chemical Engineering Hanyang University

1. Introduction

APG(Alkyl polyglycosides) known as favorable dermatological propertic nonionic surfactants can be synthesized from renewable raw materials as sugar or starch and fatty alcohol.  APG have resulted in their growing use in consumer products, excellent performance properties such as detergent, cleaning agents and cosmetics, and are distinguished by particularly advantageous ecotoxicological compatibility which predestines them for use in a number of field.  Todays, The derivatization of alkyl polyglycosides is currently being pursued with great aim and commitment in the present study.

A broad range of alkyl polyglycosides derivatives can be obtained by using nucleophilic substitution.  The reaction to ester, ether or ethoxy lates, ionic alkyl polyglycosides derivatives, such as sulfates and phophates, can be synthesized.

Among derivatives, sucrose esters are being commercially produced for the food industry. In the early 1960s, sucrose esters led to the production of large quantities of emulsifiers in cakes, biscuits, chocolates, candy, ice cream etc, and as stabilizers and wetting agents were produced for use as detergent surfactants, solubilizers for pooly water soluble drugs.

As reference of sucrose esters properties, we prepared alkyl polyglycosides butyryl esters supposed to similar character of sucrose esters, comparatively short synthesis process time.  The various character and application effect have been partially investigated as well.

2. Experimental

Materials

D-(+)-Glucose as hydrophilic material and 1-octanol, 1-decanol, butyryl chloride as hydrophobic materials, DMF(dimethyl formamide) as organic solvent were purchased from Aldrich.  P-toluenesulfonic acid as catalyst was from shinyo, magnesium oxide as a counteragent was from kanto.

Synthesis

- Alkyl polyglycosides

As Mansfield method, D-(+)-Glucose and alcohols of 2 species (1-octanol, 1-decanol) were synthesized by acetalization in decompression(110 -120℃ temperature), After reacted APG were neutralized, excessed alcohol was distilled in high vaccum.

- Alkyl polyglycosides butyryl esters

8g(24mmol) APG sample was placed in a 2-neck flask.  APG was dissolved in furified DMF(dimethyl formamide)(15ml) at a concentration of APG/100ml of DMF at room temperature and stirring on a magnetic  stirrer until the APG completely dissolved. Then 6ml of pyridine was added, and butyryl chloride was added at a fast drop rate to the APG solution.  After addition of the butyryl chloride the reaction mixture was stirred for 2-3hr at 65℃. Cooled to about 40℃, 5g of sodium bicarbonate was  mixed with 0.8g of water, and the paste was added slowly as the evolution of CO2 ceased.  The solution was then transferred to a separatory funnel and treated with diethyl ether several times. crystalline sodium sulfate was added. At this point, the reaction mixture liquid was clear and pale yellow.  Then was filtered and evaporated with temperature below 40℃. A vaccum pump was required to remove any residual solvents.

TLC showed the present only one spot.  Intramolecular bond and molecular structure, molecular weigh were analyzed into FT-IR, NMR(C13, solv chlorofrom-d), Mass spectroscopy.

3. Result and Discussion

(Properties of Butyryl esters)

Surface tension - Surface tensions □ were determined as a function of surfactant concentration(C) and temperature. surface tension was measured with Tensionmeter(KR□SS CO. K-10ST)using ring method , and range of concentration was limited from 10-5 to 10-2 mole. As expected , increasing the hydrocarbon chain decreases □cmc.

Interfacial tension - The interfacial tensions at the dodecane/surfactant solution were measured by a surface tensionmeter(KR□SS CO. K-12) using a platinum-irridium plate at room temperature.

The thermal stability in aqueous solution and stability of ester bond at    different pH - APG butyryl esters were dissolved in a solution of EtOH/H2O=1/1(V/V) to prepare concentration of 2.79□10-4M solution. The mixing solutions were thermostated at 40℃±0.1℃ exposing uv radiation to promote decomposition of the derivations and were taken at 4hr intervals for 40 hours. APG butyryl esters were observed in different pH values (pH3, pH5, pH7) for stability of synthesied ester bond at 12hr intervals during 7days.

APG butyryl esters were synthesized as referance already known the sucrose esters procedure according to Williamson synthesis method. They are confimed as adapted surfactant with various analysis method and properties experiment of tention test etc, and cmc, tension decreased as alkyl chain length.

4. References

1.Chortyk, O.T. ,Pomonis and J.G.,Johnson, A.W. :J. Agric. FoodChem .,44   ,1551 -1557(1996)

2.Allen, D., Oriol, P. and Nuria : U.S.PATENT, 6,043,203 (1998)

3.Hill, K., von Rybinski, W. and Stoll, G. : Alkyl Polyglycosides, VCH    (1996)

4.Ishitobi, M. and Kunieda, H. : Colloid Polym Sci,278,899-904(2000)

5.Bolzinger, M.A.,Grossiord, J.L. and Poelman, M.C. : Langmuir ,15 ,2307   -2315,(1999)

6.Rosen, milton J. Surfactants and interfacial phenomena 2nd ed.: John &   Sons, Inc. 226.(1989)

7.Rosen, milton J. Surfactants and interfacial phenomena 2nd ed.: John &   Sons, Inc. 213.(1989).

Fig 1. Synthetic scheme of alkyl polyglycosides butyryl esters

Fig 2. The surface tension of alkyl polyglycosides                 butyryl esters at 25℃