Diglycerol for Ester Production

Nonionic surfactants are added to a variety of consumer products to perform many functions such as emulsification, wetting, foaming, thickening, dispersion, and solubilization. Although they are much milder than ionic surfactants, they still suffer from many disadvantages. Concerns with ethoxylates range from the possible presence of residual monomers, to degradation during storage, especially in the presence of UV light. They also biodegrade slowly. Other surfactants, such as polysorbate derivatives1, may have limited use on damaged skin. Another concern is the possible presence of toxic nitrosamines in some raw materials. These may be generated during the manufacture of amine oxides, for example, or during storage and use of raw materials if small amounts of unreacted secondary amine impurities are present in the product. These issues led to the increasing use of the more innocuous glycerol and polyglycerol fatty acid esters. Biocompatible and biodegradable, fatty acid esters have overcome many of the concerns listed above.

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Solvay Interox

DIGLYCEROL

Product Data Sheet

Polyglycerol esters function not only as emulsifiers, dispersants, and spreading agents, but are also used as fragrance carriers, emollients, and cosmetic oils. Due to the innocuous nature of glycerol and polyglycerol esters, and with the hygienic advantages they offer, formulators have developed technologies that allow the use of these products in a wide range of industries, including cosmetics and food, as well as in a variety of technical applications.

Production
The polyglycerol moiety in esters is traditionally obtained by alkaline polycondensation of glycerol. This process tends to reduce the consistency and purity of these products. In contrast, Solvay Diglycerol is manufactured by a process that eliminates many of these drawbacks. Solvay does not produce diglycerol esters. (See technical data sheets DGL-01-001 and 002 for detailed information on the properties of Solvay Diglycerol.)
q

Solvay Diglycerol has a narrow oligomer distribution. It contains a minimum of 92% diglycerol and a very small amount of glycerol and triglycerol. In contrast, polyglycerol-2 products can have up to 40% glycerol for the same average molecular weight. This enhances the properties of diglycerol esters vs. polyglycerol-2 esters.
100 90 80 70 Solvay Diglycerol (MW=168) Condensation Polyglycerol-2 (MW=168)

Abundance (%)

60 50 40 30 20 10 0 Glycerol Diglycerol Triglycerol Tetraglycerol Pentaglycerol Hexaglycerol

Glycerol Oligomer

The properties of esters made from Solvay Diglycerol are further enhanced by the low content of cyclic and branched oligomers in the product, as discussed below.
10 9 8 7 Solvay Diglycerol (MW=168) Condensation Polyglycerol-2 (MW=168)

Abundance (%)

6 5 4 3 2 1 0 Cyclic Branched

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q q

The low variability of Solvay Diglycerol composition allows the production of esters with consistent quality. Due to its high purity, Solvay Diglycerol is practically odorless and colorless and generates esters of comparable purity.

In addition, Solvay Diglycerol is guaranteed free from material obtained from animal sources and is Kosher certified. Solvay Diglycerol is also free from material obtained from genetically modified organisms (GMO)2.

Properties
The properties of diglycerol fatty acid esters depend upon: q Nature of the fatty acid chosen, such as chain length, degree of unsaturation, and additional functionalities. q Degree of esterification. q Position of the hydroxyl groups esterified, such as terminal, or vicinal. The following discussion will focus mainly on the advantages of diglycerol fatty acid esters vs. other polyglycerol or glycerol esters in a variety of applications.

Surface activity
Diglycerol esters can be used as emulsifiers and thickeners in many applications. Being a small hydrophilic molecule, diglycerol generates esters that have intermediate properties between glycerol and polyglycerol esters. Diglycerol esters are more lipophilic than the corresponding polyglycerol derivatives, but more hydrophilic than the equivalent glycerides. They can be used as primary emulsifiers or co-emulsifiers in W/O or O/W formulations or in multiple emulsions. As emulsifiers, diglycerol esters offer many advantages. q Gel network structures prepared with diglycerol monoesters (e.g., diglycerol monostearate) form -crystal gel phases which remain stable at room temperature. On the other hand, the corresponding glycerides are polymorphic and transform over time to -crystal structures. This gives diglycerol esters the following advantages:
s

Better emulsification properties since -crystals have a lower ability to stabilize emulsions, a key advantage in food and cosmetic applications. s Longer formulation shelf life. s Higher viscosity of the external water phase, leading to enhanced stabilization of O/W emulsions or foams. For example, diglycerol monododecanoate produces very stable foam and has the same detergency as conventional ether-type nonionics3. In some systems, diglycerol esters have a better surface activity than the equivalent glycerol4 and propylene glycol derivatives. They can also exhibit interfacial properties comparable to those of polysorbates5. The following results were obtained using a 0.1% ester solution in Miglyol 812N (caprylic-/capric acid triglycerides) and water.
25 no emulsifier propylene glycol C16/C18 monoester

Interfacial tension (mN/m)

distilled glycerol monostearate 20

Solvay Diglycerol C16/C18 monoester 15

10 5 15 25 35 45 55 65

Time (min)

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At high water concentrations (90%), diglycerol monoesters can form multi-lamellar liposomes4, whereas the corresponding glycerol esters form cubic and reversed hexagonal mesophases in water5 (e.g., the monooleate derivatives.) The minimal content of cyclic oligomers in Solvay Diglycerol further enhances the emulsification properties of its esters. The following results were obtained using the same system previously described.
25 no emulsifier cyclic diglycerol stearate 20

Interfacial tension (mN/m)

15 Solvay Diglycerol stearate 10

0 5 15 25 35 45 55 65

Time (min)

The unique properties of diglycerol fatty acid esters discussed above give them several advantages in various applications.

Cosmetic applications
Like other nonionics, diglycerol esters are milder to the skin than anionic surfactants, and are of particular interest in skin sensitive products. They do, however, have unique properties that make them the emulsifiers of choice in many formulations.
q

q q

q q

Diglycerol esters such as diglycerol ricinoleate or isostearate make very stable W/O emulsions, even with a very high water content. Unlike other W/O systems, this allows the formation of a hydrophobic pellicule on the skin, without leaving a greasy feeling. Being more hydrophilic than the corresponding glycerides, diglycerol esters rinse more easily. For example, diglycerol monooleate is soluble in water whereas the glycerol derivative is oil soluble6. This feature is particularly valuable as diglycerol esters are excellent refatting agents in creams and lotions. This eliminates the need to add oil to the formulation, which therefore rinses off easily without leaving a heavy residue. Due to the generation of stable gel network structures, diglycerol esters are significant viscosity builders in surfactant-based systems. The ability of diglycerol esters to form liquid or liquid crystalline lipid phases gives them unique advantages in solubilizing or dispersing biologically active materials such as peptides and proteins7. These materials can be protected from degradation when solubilized or dispersed in such a fashion (e.g., diglycerol monocaprate.) Unlike some monoglycerides, the corresponding diglycerol monoesters conform with the general stability requirement of a drug formulation, i.e., no crystallization at 15C, to allow room temperature storage and use (e.g., oleic/linoleic monoesters)7. As diglycerol esters exhibit very mild moisturizing properties, they can be used as skin conditioning emollients in skin care formulations and special lipsticks (for dry lips)8. Due to their high purity, esters made from Solvay Diglycerol can be used in transparent personal care formulations.

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Food applications
Emulsifiers are commonly used in many food products, and diglycerol esters are authorized for use as food emulsifiers in many countries (see Regulatory Section for details.) Diglycerol esters have superior properties vs. the corresponding glycerol or polyglycerol esters in many food applications, especially in baking.
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Hydrated paste emulsifiers made from diglycerol monoesters (e.g., diglycerol monostearate) retain their efficacy for several weeks. On the other hand, the glycerol derivatives are only stable for a few days due to the greater stability of the diglycerol esters -crystal gel phases described above. This is particularly beneficial in baking. Fresh gels made from esters based on Solvay Diglycerol have equivalent performance to those made by corresponding glycerides.
Glycerol Monostearate Solvay Diglycerol Monostearate

No emulsifier

Dough density: 0.76 g/cm 3

Dough density: 0.41 g/cm 3

Dough density: 0.42 g/cm 3

Crumb density: 0.93 g/cm 3

Crumb density: 0.21 g/cm 3

Crumb density: 0.23 g/cm 3

Eight week old gels made from esters based on Solvay Diglycerol have superior performance vs. the corresponding glycerides.
Solvay Diglycerol Monostearate

No emulsifier

Glycerol Monostearate

Dough density: 0.76 g/cm3

Dough density: 0.94 g/cm 3

Dough density: 0.43 g/cm 3

Crumb density: 0.93 g/cm 3

Crumb density: 0.68 g/cm 3

Crumb density: 0.24 g/cm 3

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Diglycerol esters have superior heat stability vs. the corresponding glycerides9. The low content of glycerol and cyclic diglycerol oligomers is believed to be the main reason for the better performance of esters made from Solvay Diglycerol vs. condensation polyglycerol-2 esters in baking. The following results were obtained using fresh gels.

Solvay Diglycerol Monostearate

Cyclic Diglycerol Monostearate

Polyglycerol-2 Monostearate

Dough density: 0.40 g/cm 3

Dough density: 0.71 g/cm 3

Dough density: 0.48 g/cm 3

Crumb density: 0.22 g/cm 3

Crumb density: 0.37 g/cm 3

Crumb density: 0.27 g/cm 3

Due to its high purity, Solvay Diglycerol produces esters that have improved taste vs. traditional polyglycerol ester products.

Industrial applications
Glycerol and polyglycerol esters have been used in a variety of industrial applications for many years. One of their key advantages is their acceptance for food use in many countries. This is of special interest in applications involving food contact, such as lubrication of food equipment or incorporation in films for food packaging and agriculture. In addition, they are highly biodegradable.
q

As lubricants, diglycerol esters offer the following advantages: s Stability to oxidation10. s Higher thermal stability than the corresponding glycerides9. s Discoloration starts at a high temperature11. s Low volatility. Diglycerol esters are excellent antifogging/antistatic agents for PVC and polyolefin films, due to their following properties12,13: s Long lasting antifogging effects. s Low migration in the polymer. s Good resistance to removal by water. s Good compatibility with other additives (especially important in PVC). s Stabilizing effects against the thermal degradation of PVC. Derivatization of diglycerol esters offers a larger variety of possibilities vs. their equivalent glycerides.

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Regulatory Status
q

United States

Diglycerol esters are listed in the Dictionary of Cosmetic Ingredients. Esters made from Solvay Diglycerol are not approved by the US Food and Drug Administration for food use under 21 CFR 172.854 or for incorporation in polyolefin films under 21 CFR 177.1520. A GRAS (Generally Recognized As Safe) notification for esters made from Solvay Diglycerol for these applications is currently under preparation.

European Union

Solvay Diglycerol complies with EU polyglycerol specifications for use of polyglycerol esters in food under EU Commission Directive number 98/86/EC (E 475 and E 476) of November 11, 1998 on food additives other than colors and sweeteners. Esters made from Solvay Diglycerol are approved for addition to food-contact materials under EU Directive number 95/3/EC of the European Parliament and Council of Europe of February 23, 1995 on plastic materials and articles intended to come into contact with foodstuffs.

Japan

Diglycerol esters are listed in The Japanese Standards of Cosmetic Ingredients. Diglycerol esters are approved for use as food emulsifiers, and have been registered in the list of Food Hygiene Act of Japan under Registration No.80 (registration date: July 31, 1957).

References
1 R.S. Lanigan, Final Report on the Safety Assessment of PEG-20 Sorbitan Cocoate; PEG-40 Sorbitan Diisostearate; PEG-2, -5, and -20 Sorbitan Isostearate; PEG-40 and -75 Sorbitan Lanolate; PEG-10, -40, -44, -75,and -80 Sorbitan Laurate; PEG-3, and -6 Sorbitan Oleate; PEG-80 Sorbitan Palmitate; PEG-40 Sorbitan Perisostearate; PEG-40 Sorbitan Peroleate; PEG-3, -6, -40, and -60 Sorbitan Stearate; PEG-20, -30, -40, and -60 Sorbitan Tetraoleate; PEG-60 Sorbitan Tetrastearate; PEG-20 and -160 Sorbitan Triisostearate; PEG-18 Sorbitan Trioleate; PEG-40 and -50 Sorbitol Hexaoleate; PEG-30 Sorbitol Tetraoleate Laurate; and PEG-60 Sorbitol Tetrastearate - Addendum to the Final Report on the Safety Assessment of Polysorbates, in F.A. Anderson (ed.), Safety Assessment of Cosmetic Ingredients, International Journal of Toxicology, 2000, 19(2), 43-89 (Report issued by Cosmetic Ingredient Review panel). 2 At the moment, the glycerol used to make Solvay Diglycerol is either synthetic or biodiesel glycerol. The latter is a coproduct of biodiesel production obtained by transesterification of rapeseed oil certified from countries where crops of genetically modified rape are forbidden. 3 S. Matsumura, M. Maki, K. Toshima, and K. Kawada, Enzymatic Synthesis, Surface Activity, Antimicrobial Properties and Biodegradability of Diglycerol and Triglycerol Fatty Acid Esters, Nihon Yukagakkaishi, 1999, 48(7), 681-692. 4 J. Holstborg, B.V. Pedersen, N. Krog, S.K. Olesen, Physical Properties of Diglycerol Esters in Relation to Rheology and Stability of Protein-Stabilized Emulsions, Colloids And Surfaces B: Biointerfaces, 1999, 12(3-6), 383-390. 5 S.K. Olesen, and N. Krog, Phase Behaviour of New Food Emulsifiers and their Application, in K.G. Berger, Oils and Fats in Food Applications Proceedings of the Food Applications Session of the 22 nd Congress of the International Society of Fats Research (ISF), Kuala Lumpur, Malaysia, 7-12 September 1997. 6 J. Chen, and E. Dickinson, Effect of Monoglycerides and Diglycerol Esters on Viscoelasticity of Heat-Set Whey Protein Emulsion Gels, International Journal of Food Science and Technology, 1999, 34, 493-501. 7 WO 98/30206, publ. July 16, 1998, Controlled Release Composition. 8 JP 7223925, publ. August 22, 1995, Lip Cosmetics Containing Reaction Products of Diglycerin Esters with Dicarboxylic Acids. 9 T. Ushikusa, T. Maruyama, I. Nhya, and M. Okada, Pyrolysis Behaviors and Thermostability of Polyglycerols and Polyglycerol Fatty Acid Esters, J. Jpn. Oil Chem. Soc., 1990, 39(5), 314-320. 10 JP 7173480, publ. July 11, 1995, A Lubricating Oil Composition which is Safe with Respect to Food. 11 JP 2000178229, publ June 27, 2000, Polyhydric alcohol fatty acid esters for polymer additives having excellent heat stability, moldability, and improved odor. 12 US 3,558,537, publ. January 26, 1971, Imparting Antifogging Properties to PVC Resins and Compositions Therefore. 13 US 5,030,280, publ. July 9, 1991, Use of Nonionic Surfactants for Preventing the Fogging of Plastic Surfaces and Preparations Containing These Surfactants.

To our actual knowledge, the information contained herein is accurate as of the date of this document. However, neither Solvay Interox, Inc. nor any of its affiliates makes any warranty, express or implied, or accepts any liability in connection with this information or its use. This information is for use by technically skilled persons at their own discretion and risk and does not relate to the use of this product in combination with any other substance or any other process. This is not a license under any patent or other proprietary right. The user alone must finally determine suitability of any information or material for any contemplated use, the manner of use and whether any patents are infringed. Please note that diglycerol esters are not part of the business of Solvay Interox, Inc. and its affiliates, but may be a business of other companies potentially also owning related intellectual property rights. No warranty is made and no liability is taken whatsoever by Solvay Interox, Inc. with regard to the freedom to use any of the information given herein on diglycerol esters.

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DIGLYCEROL

Product Data Sheet