NL2007240C2 - Sugar-based plasticizers. - Google Patents
Sugar-based plasticizers. Download PDFInfo
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- NL2007240C2 NL2007240C2 NL2007240A NL2007240A NL2007240C2 NL 2007240 C2 NL2007240 C2 NL 2007240C2 NL 2007240 A NL2007240 A NL 2007240A NL 2007240 A NL2007240 A NL 2007240A NL 2007240 C2 NL2007240 C2 NL 2007240C2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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Description
SUGAR-BASED PLASTICIZERS FIELD OF THE INVENTION
The present invention relates to plasticizers and coalescents, and to methods for 5 producing new compounds for use as plasticizers and coalescents.
BACKGROUND OF THE INVENTION
Plasticizers (or “dispersants”) are compounds that are added to polymer-based material compositions, such as plastics, adhesives and paints, to reduce the glass transition 10 temperature (Tg) of these compositions. The use of plasticizers results in an increase of flexibility (elasticity), processability and durability of plastics, which greatly broadens their application possibilities and allows tuning of their properties. In terms of production volumes, plasticizers form the most important plastics additive. About 90% of all plasticizers are applied in polyvinyl chloride (PVC). “Hard” PVC is used in drain 15 pipes and window frames. “Plasticized” PVC may contain up to 60 phr (parts per hundred rubber) of plasticizer, and is applied in, for example, vinyl flooring and rain gear. Phthalate esters form by far the largest class of plasticizers for use in plastics, making up a share of around 84% of the world plasticizer market. Generally, phthalate ester plasticizers owe their popularity to a combination of low price, versatility and 20 excellent technical performance. At present, about 15 different phthalate plasticizers are being produced commercially; of these, n-butylbcnzyl phthalate (BBP), di-n-butyl phthalate (DnBP, DBP), di-2-ethylhexyl phthalate (DEHP) and di-isononyl phthalate (DiNP) are the most commonly applied plasticizer compounds.
In coating formulations such as latex paint, plasticizers such as 2,2,4-trimethyl-25 1,3-pentanediol monoisobutyrate (Texanol™; Eastman, USA) are incorporated to reduce the glass transition temperature (Tg) of the latex formulation below that of the drying temperature, enabling the formation of a continuous film as the coating cures. In the art, such temporary plasticizers are commonly referred to as “coalescing agents” or simply “coalescents”. Plasticizers are not covalently bound to the material to which 30 they are added; as a result, during production, usage and disposal of plasticized materials, plasticizer compounds are emitted to the surroundings due to migration and subsequent leaching and evaporation. As the use of phthalate ester plasticizers is intense and ubiquitous, ranging from baby toys to food packaging to medical 2 disposables to floor covering, there are growing concerns regarding the safety of longterm phthalate exposure. Phthalate esters and their metabolites have been detected in food products such as milk, meat and baby food, and are accumulated in the fat tissue and milk of mammals. Phthalate ester plasticizer accumulation in the body has been 5 associated with negative health effects including endocrine disruption, carcinogenicity, insulin resistance, low birth weight and even attention deficit hyperactivity disorder (ADHD). Accordingly, the European Union has recently imposed a ban on the use of n-butylbenzyl phthalate (BBP), di-n-butyl phthalate (DnBP, DBP) and di-2-ethylhexyl phthalate (DEHP) in children’s toys and other children’s articles, and on the use of di-10 isononyl phthalate (DiNP) and di-isodecyl phthalate (DiDP) in all articles for children under the age of 3 years.
Likewise, in the field of coatings, coalescing agents are under increasing scrutiny by safety, environmental and health institutions, as the long-term exposure to man-made volatile organic compounds (VOCs) is linked to several adverse respiratory, 15 allergic and immune effects.
The increasing pressure from legislation to reduce the use of harmful and/or volatile coalescing agents and plasticizers as described herein above has motivated the development of alternative compounds capable of reducing the glass transition temperature (Tg) of the composition to which they are added. Commercially available 20 alternative plasticizing/coalescing compounds comprise adipates such as bis(2-ethylhexyl) adipate (DEHA) benzoates such as diethylene glycol dibenzoate (DEGDB), alkyl citrates such as triethyl citrate (TEC) and acetyl tri-n-butylcitrate (ATBC), trimellitates (esters of 1,2,4-benzenetricarboxylic acid), sulfonates, phosphates and polymeric plasticizers such as polycaprolactone-polycarbonate (PCL-PC). A plasticizer 25 comprising fully acetylated 1,2-hydroxystearic acid glycerol monoester, prepared by esterification of glycerol and castor oil is commercially available as GRINDSTED® SOFT-N-SAFE. EP1058711B1 discloses isosorbide esters, including isosorbide-2,5-di-2-ethylhexanoate (IsDEH) for reducing the glass transition temperature of vinyl and styrene acrylic latex coating compositions and PVC plastic.
30 Alternative solutions to the problem of plasticizer migration and leaching have been sought in the field of surface modification of the polymeric material comprising the plasticizing agent. However, each of these alternative compounds and methods aimed at reducing migration, leakage and bioaccumulation suffer from one or more 3 disadvantages including high volatility, high price, unsatisfactory thermal stability, insufficient versatility, poor hydrolytic stability, modified transparency/opacity, objectionable odor, limited availability and/or reduced effectiveness. For example, while trimellitate plasticizers show less volatility and migration than phthalates, they 5 adversely affect the transparency of PVC foils in which they are incorporated. Citrate plasticizers and coalescents have a favorable toxicological profile; however, this is thwarted by limited thermal stability and increased sensitivity towards microbial decay.
Thus, there is a need in the art for new compounds that form suitable alternatives to the phthalate esters, which compounds are able to reduce the glass 10 transition temperature of the composition to which they are added, but do not suffer from the above-described disadvantages associated with phthalate esters and their present alternatives, and which compounds are environmentally and physiologically safe.
15 SUMMARY OF THE INVENTION
It is an object of the present invention to provide plasticizers and coalescing agents that do not suffer from the disadvantages summarized herein above. In particular, it is an object of the present invention to provide compounds that are able to reduce the glass transition temperature of the composition to which they are added, that 20 are safer for living organisms and show improved biodegradability. It is a further object to provide materials having plasticizing and coalescing properties that are thermally stable and display limited volatility during processing and use.
The inventors have now found that particular substituted glycosides, more precisely O-acylated monoglycosides, obtainable by O-glycosidation at the anomeric 25 carbon atom of a monosaccharide and acylation (alkanoylation) of its remaining non-anomeric hydroxyl groups, are capable of significantly reducing the glass transition temperature of thermoplastic polymers. A comparison is attached in the Examples section. Hence, the substituted glycosides according to the present invention can be successfully used as a plasticizer in synthetic plastics comprising polyvinyl chloride 30 (PVC), polyvinyl acetate (PVA), rubbers, cellulose plastics, and polyurethane (PU) and polymeric foams, as well as in adhesives, sealants and in coating compositions which cure by coalescence, like inks and acrylic and styrene-acrylic dispersions in water.
4
The substituted glycosides of the invention are found to be highly compatible with mainstream plastics like PVC even up to levels of 60 phr (“(weight) parts per hundred of rubber”). In addition, they are found to be readily applicable as coalescing agent in customary commercial coating formulations, particularly water-based latex-5 type compositions. Notably, when mixed in an amount of 20 % (w/w) into PVC they are capable of reducing its glass transition temperature (Tg) with more than 40 °C.
Furthermore, the plasticizing/coalescing compounds according to the invention display thermal stability and volatility comparable to those of state of the art phthalate p lasticizers/co ales cents.
10 Accordingly, in one aspect the present invention relates to particular substituted monoglycosides. In another aspect, the invention relates to the use of these substituted monoglycosides as plasticizers and coalescing agents. More specifically, the invention relates to O-acylated O-glycosides, including glycopyranosides and glycofuranosides, wherein the anomeric carbon is O-glycosidated using a linear, cyclic or branched, 15 saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon aglycon moiety “R1”. In these compounds, the remaining available (non-anomeric) hydroxyl groups of the glycosidated monosaccharide are acylated, i.e. the hydrogen atom of the hydroxyl group is replaced with an acyl group R2’ wherein R2 corresponds to an acyl radical RC=0. Examples include O-acetylation (R = CH3) and O-20 propionylation (R = CH3CH2). Without wishing to be bound to any theory, it is the belief of the inventors that acylation of the free hydroxyl groups reduces the polarity of the R1 O-glycosides and improves compatibility with the polymeric matrix to be plasticized. Throughout this text, the O-acylated and O-glycosidated monosaccharide derivatives described above will be referred to as “R, R -substituted 25 (mono)glycosides” or simply “substituted glycosides”.
The invention furthermore pertains to a method of reducing the glass transition temperature (Tg) of a composition comprising a thermoplastic polymer, comprising adding an effective amount of the substituted monoglycosides of the invention to said composition.
30 In another aspect a method of preparing the substituted glycosides according to the invention is provided. Advantageously, the substituted glycosides of the invention may be prepared starting from the cracking products of the biorefinery of agricultural side streams, including wheat, com (maize) and sugar beet pulp. For instance, sugar 5 beet pulp, the residual tissue after beet sugar production, contains over 70 wt% of polysaccharides, which are predominantly built from glucose, galacturonic acid, arabinose, xylose, and galactose monosaccharide units. Hence, the present invention provides a novel means for utilizing the residual material of food production.
5 As the plasticizing/coalescing compounds of the present invention are derived from naturally occurring sugars, they have great potential as environmentally and physiologically safe additives for application in e.g. food packaging, baby products and children’s toys. In one aspect, the invention thus pertains to a polymer-based consumer good comprising an effective amount of the substituted glycosides, i.e. present to an 10 extent that a desirable Tg reducing and/or coalescing effect in the consumer good is attained.
LIST OF PREFERRED EMBODIMENTS
1. A substituted glycoside having the general structure 15 (I) R3 H-C-O OR1 [R2°—CHlx/C\4 wherein x is 2 or 3; R1 is a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon having from 1 to 22 carbon atoms; 20 R2 is an acyl group RC=0, wherein R is a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon having from 1 to 22 carbon atoms; R4 is H or CH2OR2; and wherein if x = 2 and R4 is H, R3 is CH(OR2)R5, and R5 represents H, COOR1 or 25 CH2OR2; 6 wherein if x = 2 and R4 is CH2OR2, R3 is CH2OR2; wherein if x = 3 and R4 is H, R3 is selected from the group consisting of H, COOR1, and CH2OR2; wherein if x=3 and R4 is CH2OR2, R3 is H.
5 2. Substituted glycoside according to embodiment 1, wherein R1 is selected from the group consisting of methyl (CH3), ethyl (C2H5), n-propyl (n-C3H7), iso-propyl (i-C3. H7), n-butyl (n-C4H9), iso-butyl (L-C4H9), n-pentyl (n-CsHn), iso-pentyl (i-CsHn), hexyl (C’V.Hifr, 2-ethylhexyl (CH2CH(C2H5)C4H9), n-octyl (CsHn), iso-nonyl (C9H19), i-CioH2i (iso-decyl) and n-dodecyl (n-Ci2H25), preferably ethyl, n-butyl, i-butyl and i-10 pentyl.
3. Substituted glycoside according to embodiment 1 or 2, wherein R2 is selected from the group consisting of acetyl (CH3C=0), propionyl (CH3CH2C=0), butyryl (CH3(CH2)2C=0) and pentanoyl (CH3(CH2)3C=0), preferably CH3C=0 (acetyl) and propionyl (CH3CH2C=0).
15 4. Substituted glycoside according to any one of the preceding embodiments, wherein the substituted glycoside is an arabinofuranoside, xylofuranoside, galacturonic acid furanoside, fructofuranoside, arabinopyranoside, xylopyranoside, galacturonic acid pyranoside or fructopyranoside.
5. Substituted glycoside according to embodiment 4, wherein the substituted 20 glycoside is an arabinoside.
6. Substituted glycoside according to embodiment 5, wherein the substituted glycoside is chosen from O-propionylated ethyl L-arabinoside (PrEA), O-propionylated i-pentyl L-arabinoside (PriPnA), O-acetylated ethyl L-arabinoside (AEA), O-propionylated n-butyl L-arabinoside (PrBA), O-acetylated n-butyl L-arabinoside 25 (ABA), O-propionylated i-butyl L-arabinoside (PriBA), O-acetylated i-butyl L-arabinoside (AiBA) or O-acetylated i-propyl L-arabinoside (AiPA).
7. Substituted glycoside according to any one of the preceding embodiments having a degree of acylation of at least 70%, preferably at least 80%, more preferably at least 85%, most preferably at least 90%.
30 8. A plastic, coating, ink, adhesive or sealant composition comprising at least a thermoplastic polymer and one or more substituted glycosides according to embodiments 1-7.
7 9. Composition according to embodiment 8, containing at least 0.5 wt%, based on weight of the thermoplastic polymer, of the one or more substituted glycosides.
10. Composition according to embodiment 8 or 9, having a glass transition temperature lower than 80 °C, preferably lower than 40 °C, more preferably lower than 5 30 °C, even more preferably lower than 25 °C, yet even more preferably lower than 20 °C, yet even more preferably lower than 15 °C, most preferably lower than 5 °C.
11. Composition according to any one of embodiment 8-10, wherein the composition contains 5-99.5 wt.% of a thermoplastic polymer selected from polyvinyl chloride (PVC), polystyrene (PS), poly(vinyl butyral) (PVB), poly(vinyl acetate) 10 (PVA), nylon, polyamide, polycelluloid, poly(methyl methacrylate) (PMMA), vinyl acrylic copolymer, styrene/butyl acrylic/methacrylic acid copolymer and combinations thereof.
12. A process of preparing a composition according to any one of embodiments 8-11, said process comprising combining a thermoplastic polymer with an additive, said 15 additive containing at least 5 wt.% of substituted glycoside according to any one of embodiments 1-7.
13. Use of a substituted glycoside according to any one of embodiment 1-7, or mixtures thereof, as a plasticizer or coalescing agent in a composition comprising a thermoplastic polymer.
20 14. A method of preparing a substituted glycoside according to any one of embodiments 1-7, comprising the steps, in no particular order, of O-glycosidation at the anomeric carbon of a monosaccharide or monosaccharide derivative to produce an R1-O-monoglycoside; O-acylation of the non-anomeric hydroxyl groups of said monosaccharide or 25 monosaccharide derivative to produce the corresponding OR2 ester, wherein R1 is a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon having from 1 to 22 carbon atoms; and R2 is an acyl group RC=0, wherein R is a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon having 30 from 1 to 22 carbon atoms.
15. Method according to embodiment 14, comprising the consecutive steps of (i) glycosidation of a monosaccharide in the presence of a catalyst, to produce an R1-O-glycoside; 8 (ii) acylation of the available non-anomeric hydroxyl groups of said R'-O-glycoside to produce an O-acylated R1-O-glycoside.
DETAILED DESCRIPTION OF THE INVENTION 5 In one aspect the invention thus pertains to a substituted glycoside having the general structure (I) R3 H-C-O OR1 [r2°—chJx;C\4 wherein x is 2 or 3; 10 R1 is a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon having from 1 to 22 carbon atoms; R2 is an acyl group RC=0, wherein R is a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon having from 1 to 22 carbon atoms; 15 R4 is H or CH2OR2; and wherein if x = 2 and R4 is H, R3 is CH(OR2)R5, and R5 represents H, COOR1 or CH2OR2; wherein if x=2 and R4 is CH2OR2, R3 is CH2OR2; wherein if x = 3 and R4 is H, R3 is selected from the group consisting of H, 20 COOR1, and CH2OR2; wherein if x=3 and R4 is CH2OR2, R3 is H.
Within the context of the present invention, the terms “substituted glycoside”, and “(R2) acylation” should be understood to refer to compounds wherein preferably at 25 least 60% of the available non-anomeric hydroxyl groups of the monoglycoside starting 9 material are esterified with an acyl group R2, with R2 as defined above, i.e. to compounds having a degree of R2 acylation, or briefly “acylation degree” of 60% or more. The acylation degree may be determined by saponification of the acylated glycoside and quantification, e.g. using HPLC, of the amount of acid produced on 5 hydrolysis of the glycoside ester. From this, the amount of unsubstituted glycoside is calculated and subsequently the degree of substitution (DS) of the glycoside. The acylation degree corresponds to DS divided by the number of hydroxyl groups in the glycoside that are theoretically available for acylation. Preferably, the acylation degree of the substituted glycosides of the invention is at least 70%, more preferably at least 10 80%, even more preferably at least 85%, most preferably at least 90%.
Within the context of the present invention, the term “plasticizer” refers to a compound that is capable of increasing the plasticity or fluidity of the material composition in which it is incorporated. Although various theories about the mechanism of plasticizing action exist, it is generally accepted that plasticizer 15 molecules are to a smaller or larger extent capable of embedding themselves between the (polymeric) molecules of the composition in need of plasticization, thereby reducing friction between the latter molecules, increasing “free volume” and reducing the glass transition temperature of the composition.
Herein, a “coalescing agent” or “coalescent” is considered a particular sub-20 species of the concept of plasticizer. More specifically, a “coalescing agent” reduces the glass transition temperature of a coating composition during its curing cycle, thereby facilitating fusion of the coating emulsion droplets (“coalescence”) as the solvent evaporates, resulting in satisfactory film formation. As such, a coalescing agent can be considered as a temporary plasticizing agent.
25 In another aspect, the invention pertains to the use of a substituted glycoside as defined above, or mixtures thereof, as a plasticizer or coalescing agent in a composition comprising a thermoplastic polymer.
Preferably, the substituted glycosides of the invention are used as a plasticizing or coalescing agent in plastics (including polymeric foams), coating compositions 30 (including inks), sealants and adhesives.
The R1 aglycon moiety is bonded through an O-glycosidic linkage at the anomeric position of the sugar moiety. It may optionally be substituted with heteroatoms selected from nitrogen, oxygen, sulfur or phosphor, and/or functional 10 groups chosen from esters, ethers, aldehydes and amides. Preferably, R1 is selected from the group consisting of CH3 (methyl), C2H5 (ethyl), n-C3H7 (n-propyl), i-C3H7 (iso-propyl), n-C4H9 (n-butyl), i-C4H9 (iso-butyl), n-CsHn (n-pentyl), i-C5Hn (isopentyl; CH3CH2CH(CH3)2), C6Hi3 (hexyl), CH2CH(C2H5)C4H9 (2-ethylhexyl), C8Hi7 5 (n-octyl), i-CgHig (iso-nonyl), i-CioH2i (iso-decyl) and n-Ci2H25 (n-dodecyl). In a particularly preferred embodiment, R1 is ethyl, n-propyl, n-butyl, i-butyl or i-pentyl, more preferably ethyl, n-butyl, i-butyl or i-pentyl.
The acyl group R2 aids in modulating the polarity of the glycosides. R2 may optionally be substituted with heteroatoms selected from nitrogen, oxygen, sulfur or 10 phosphor, and/or functional groups chosen from esters, ethers, aldehydes and amides. In one preferred embodiment, R2 is an acetyl (CH3C=0) or proprionyl (CH3CH2C=0) group. It was observed by the inventors that too high viscosities of the substituted glycosides impede mixing with the polymer matrix. It was furthermore found that this viscosity to at least some extent is reduced using longer chain acyl groups at the free 15 hydroxyl positions of the glycosides. Accordingly, in another preferred embodiment R2 is propionyl (CH3CH2C=0), butyryl (CH3(CH2)2C=0) or pentanoyl (CH3(CH2)3C=0).
Synthesis
The present invention also provides a method for the preparation of the substituted 20 glycosides according to the invention, comprising the steps, in no particular order, of O-glycosidation at the anomeric carbon of a monosaccharide or monosaccharide derivative to produce an R1-O-monoglycoside; O-acylation of the non-anomeric hydroxyl groups of said monosaccharide or • • • »2 monosaccharide derivative to produce the corresponding OR ester.
25 Preferably, the substituted glycoside compounds of the invention are prepared according to a process comprising the subsequent steps of (i) glycosidation at the anomeric carbon of a monosaccharide in the presence of a catalyst, to produce an R1-O-glycoside; (ii) acylation of the available non-anomeric hydroxyl groups of said R'-O-30 glycoside to produce an O-acylated R1-O-glycoside.
Herein, R1 is a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon having from 1 to 22 carbon atoms. R1 may optionally be substituted with heteroatoms selected from nitrogen, oxygen, sulfur 11 or phosphor, and/or functional groups chosen from esters, ethers, aldehydes and amides; preferably, R1 is selected from the group consisting of CH3, C2H5, n-C3H7, n-C4H9, i-C4H9 (iso-butyl), n-C5H| 1, i-C5Hn (iso-pentyl), C6Hi3, CF^CH^Hs^Hg (2-ethylhexyl), CgHn (n-octyl), i-CgHig (iso-nonyl), i-CioH2i (iso-decyl) and n-Ci2H25 (n-5 dodecyl). In a particularly preferred embodiment, R1 is ethyl, n-propyl, n-butyl, i-butyl or i-pentyl, more preferably ethyl, n-butyl, i-butyl or i-pentyl.
R2 is an acyl group (RC=0), wherein R is a linear, cyclic or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon having r\ from 1 to 22 carbon atoms. R may optionally substituted with heteroatoms selected 10 from nitrogen, oxygen, sulfur or phosphor, and/or functional groups chosen from esters, ethers, aldehydes and amides.
In one preferred embodiment, R2 is an acetyl (CH3C=0), propionyl (CH3CH2C=0), butyryl (CH3(CH2)2C=0) or pentanoyl (CH3(CH2)3C=0) group. In a particularly preferred embodiment, R2 is acetyl (CH3C=0) or propionyl 15 (CH3CH2C=0).
Several methods are known in the art for the formation of substituted glycosides, and it is within the ordinary competence of the skilled person to select an appropriate synthesis method. Per J. Garegg, “Synthesis and Reactions Of Glycosides” in Advances in Carbohydrate Chemistry and Biochemistry, Vol. 59, its contents herein 20 incorporated by reference, provides an extensive overview of the state of the art in the synthesis of substituted glycosides.
A particularly suitable method for alkylation of monosaccharides is the Fischer glycosidation (also referred to as “Fischer glycosylation”) reaction, involving the formation of a glycoside by the reaction of an unprotected aldose or ketose with a 25 primary alcohol in the presence of an acid catalyst, resulting in the corresponding alkyl O-glycoside.
In case of the use of uronic acid monosaccharides as starting material, such as galacturonic acid, which contain a free carboxylic acid group, said carboxylic acid group is also esterified (producing the corresponding uronic ester group -COOR1) using 30 this procedure.
Provision of the substituted glycosides of the invention furthermore involves an acylation reaction, replacing the hydrogen atoms of the unsubstituted hydroxyl groups with an acyl group R2 to result in alkanoyl ester groups OR2, hence providing the O- 12 acylated glycosides according to the invention. Acylation of the glycoside may be performed by reacting with the appropriate acid anhydride or acid halide, such as propionic anhydride, (CH3CH2C=0)20 or acetyl chloride (CH3C=OCl), respectively. The acylation reaction is typically performed in the presence of a mild base such as 5 pyridine. As an environmentally benign alternative, ionic liquids may be used as solvent/catalyst in the acylation reaction. Another suitable process for providing the substituted glycosides of the invention involves the Koenigs-Knorr reaction, wherein a glycosyl halide is substituted with an alcohol in the presence of silver promoter to yield the alkyl O-glycoside. In this process, the O-glycosidation reaction is performed on the 10 O-acylated glycosyl halide, i.e., R2 substitution is performed prior to R1 substitution.
Further suitable methods include enzymatic or microbial glycosidations and the Schmidt alkylation reaction. Alternatively the acylated glycosides can be prepared via a transesterification reaction of an acyl ester (e.g. methyl ester) and the alkyl glycoside with or without the use of a suitable co-solvent.
15 As defined herein above, acylation is considered to relate to esterification of at least 60% of the available hydroxyl groups at the non-anomeric carbon atoms of the monosaccharide or monosaccharide derivative. Preferably, the acylation degree of the substituted glycosides of the invention is at least 80%, more preferably at least 85%, most preferably at least 90% 20 The pentose or hexose starting compounds may be keto- or aldo- monosaccharides. As already explained in the summary of the invention, the sugar-based plasticizing/coalescing agents of the invention may advantageously be derived from the cracking products of the biorefinery of agricultural side streams, such as sugar beet pulp or wheat bran. The pentose or hexose monosaccharide starting material is 25 preferably selected from arabinose, xylose, galacturonic acid, galactose, glucose, and fructose, more preferably from arabinose, xylose, galacturonic acid, and fructose. In the aldose and ketose derivatives having the general structure I presented herein above this corresponds to the aldofuranoside (x = 2; R4 = H) compounds wherein R3 is CH(OR2)R5, and R5 represents H (arabinose or xylose derived), COOR1 (galacturonic 30 acid derived), or CH2OR2 (glucose or galactose derived); to the aldopyranoside (x = 3; R4 = H) compounds wherein R3 is H (arabinose or xylose derived), COOR1 (galacturonic acid derived) or CH2OR2 (glucose or galactose derived), respectively; to the ketofuranoside (x=2; R4 = CH2OR2) compounds wherein R3 is CH2OR2 13 (ffucto furanoside); and to the ketopyranose (x=3; R4 = CH2OR2), wherein R4 is H (fructopyranoside). R1 and R2 are as described in detail herein above.
The glycosidation reaction may be catalyzed by homogenous or heterogeneous catalysts. Suitable homogenous catalysts are hydrogen chloride (HC1), sulfuric acid 5 (H2SO4) p-toluenesulfonic acid (p-TsOH), boron trifluoride diethyl etherate (BF3.Et20), iodine (I2) and iron(III) chloride (FeCh). Suitable heterogeneous catalysts include macroporous zeolites and acid (ion-exchange) resins like Amberlyst® 15. The substituted glycosides of the invention can be present in the pyranose (six-membered monosaccharide ring, x = 3) or furanose (five-membered ring, x = 2) form. Generally, 10 during synthesis, e.g. in the Fischer glycosidation reaction a mixture of both forms is obtained. The inventors have found that by appropriate choice of catalyst it is possible to influence the ratio of kinetic (furanoside) to thermodynamic (pyranoside) glycoside products of the alkylation reaction. As an example, using Amberlyst® 15 as acid catalyst in the glycosidations of arabinose in ethanol, arabinopyranoside and 15 arabinofuranoside were formed in a molar ratio of 61:39. This equilibrium can be shifted towards the formation of predominantly, i.e. more than 50 %, preferably more than 60 %, alkyl O-furanosides using catalysts with more Lewis acid character, such as boron trifluoride diethyl etherate (BF3.Et20) and iodine (I2). In one embodiment, trifluoride diethyl etherate (BF3.Et20) or iodine (I2) are used as a catalyst in the 20 glycosidation reaction.
Typical compounds according to the invention are acetylated methyl- L-arabinoside, acetylated ethyl-L-arabinoside, acetylated n-propyl-L-arabinoside, acetylated n-butyl-L-arabinoside, acetylated i-butyl-L-arabinoside, acetylated i-propyl-L-arabinoside, acetylated 2-ethylhexyl-L-arabinoside, acetylated octyl-L-arabinoside, 25 propionylated ethyl-L-arabinoside, propionylated n-butyl-L-arabinoside, propionylated i-butyl-L-arabinoside, propionylated i-pentyl-L-arabinoside, iso-butyrylated ethyl-L-arabinoside, iso-butyrylated n-propyl-L-arabinoside, iso-butyrylated i-propyl-L-arabinoside, iso-butyrylated i-pentyl-L-arabinoside, acetylated ethyl glycoside ester of D-galacturonic acid, acetylated n-butyl glycoside ester of D-galacturonic acid, 30 acetylated i-butyl glycoside ester of D-galacturonic acid, acetylated octyl glycoside ester of D-galacturonic acid, acetylated i-pentyl glycoside ester of D-galacturonic acid, acetylated i-propyl glycoside ester of D-galacturonic acid, acetylated n-propyl glycoside ester of D-galacturonic acid, propionylated ethyl glycoside ester of D- 14 galacturonic acid, propionylated i-propyl glycoside ester of D-galacturonic acid, propionylated n-butyl glycoside ester of D-galacturonic acid, propionylated i-butyl glycoside ester of D-galacturonic acid, propionylated i-pentyl glycoside ester of D-galacturonic acid, butyrylated octyl glycoside ester of D-galacturonic acid, butyrylated 5 ethyl glycoside ester of D-galacturonic acid, butyrylated i-propyl glycoside ester of D-galacturonic acid, butyrylated n-butyl glycoside ester of D-galacturonic acid, butyrylated i-butyl glycoside ester of D-galacturonic acid, butyrylated i-pentyl glycoside ester of D-galacturonic acid, acetylated ethyl-D-xyloside, acetylated i-propyl-D-xyloside, acetylated n-propyl-D-xyloside, acetylated i-butyl-D-xyloside, acetylated 10 n-butyl-D-xyloside, acetylated n-pentyl-D-xyloside, propionylated i-propyl-D-xyloside, propionylated n-propyl-D-xyloside, propionylated i-butyl-D-xyloside, propionylated n-butyl-D-xyloside, propionylated i-pentyl-D-xyloside, iso-butyrylated i-propyl-D-xyloside, iso-butyrylated n-propyl-D-xyloside, iso-butyrylated i-butyl-D-xyloside, iso-butyrylated n-butyl-D-xyloside, iso-butyrylated i-pentyl-D-xyloside, acetylated ethyl-15 D-fructoside, acetylated i-propyl-D-fructoside, acetylated n-propyl-D-fructoside, acetylated i-butyl-D-fructoside, acetylated n-butyl-D-fructoside, acetylated n-pentyl-D-fructoside, propionylated i-propyl-D-fructoside, propionylated n-propyl-D-fructoside, propionylated i-butyl-D-fructoside, propionylated n-butyl-D-fructoside, propionylated i-pentyl-D-fructoside, iso-butyrylated i-propyl-D-fructoside, iso-butyrylated n-propyl-20 D-fructoside, iso-butyrylated i-butyl-D-fructoside, iso-butyrylated n-butyl-D-fructoside, and iso-butyrylated i-pentyl-D-fructoside, wherein the substituted monoglycosides are present in their 5-membered (furanoside) or 6-membered (pyranoside) ring form, or as a mixture thereof
Preferred compounds according to the invention are those wherein R1 = ethyl, 25 n-butyl, i-butyl or i-pentyl; R2 = acetyl or propionyl; and for x=2 and R4 is H, R3 is CH(OR2)R5, with R5 representing H (arabinofuranoside, xylofuranoside) or COOR1 (galacturonic acid furanoside); for x=3 and R4 is H, R3 is H (arabinopyranoside, xylopyranoside) or COOR1 (galacturonic acid pyranoside); for x=2 and R4 is CH2OR2, R3 is or CH2OR2 (fructofiiranoside); for x=3 and R4 is CH2OR2, R3 is H 30 (fructopyranoside).
In another preferred embodiment, the substituted glycoside is an arabinofuranoside, xylofuranoside, galacturonic acid furanoside, fructofiiranoside, arabinopyranoside, xylopyranoside, galacturonic acid pyranoside or fructopyranoside 15
Particularly preferred compounds are arabinosides, i.e. arabinofuranosides and/or arabinopyranosides. Particularly preferred arabinosides are O-propionylated ethyl L-arabinoside (PrEA), O-propionylated i-pentyl L-arabinoside (PriPnA), O-acetylated ethyl L-arabinoside (AEA), O-propionylated n-butyl L-arabinoside (PrBA), 5 O-acetylated n-butyl L-arabinoside (ABA), O-propionylated i-butyl L-arabinoside (PriBA), O-acetylated i-butyl L-arabinoside (AiBA) or O-acetylated i-propyl L-arabinoside (AiPA).
Much preferred compounds are O-propionylated ethyl L-arabinoside (PrEA), 0-propionylated i-pentyl L-arabinoside (PriPnA), O-acetylated ethyl L-arabinoside 10 (AEA), O-propionylated n-butyl L-arabinoside (PrBA), O-propionylated i-butyl L-arabinoside (PriBA) and O-acetylated n-butyl L-arabinoside (ABA).
In a further aspect, the invention pertains to a plastic, coating, ink, adhesive or sealant composition comprising at least a thermoplastic polymer and an effective 15 amount of one or more of the alkyl glycosides of the invention. Preferably, the composition contains at least 0.5 wt%, more preferably at least 1 wt%, even more preferably at least 5 wt%, yet even more preferably at least 10 wt%, most preferably at least 20 wt%, based on weight of the thermoplastic polymer, of the one or more substituted glycosides of the invention. Preferably, the composition has a glass 20 transition temperature lower than 80 °C, preferably lower than 40 °C, more preferably lower than 30 °C, even more preferably lower than 25 °C, yet even more preferably lower than 20 °C, yet even more preferably lower than 15 °C, most preferably lower than 5 °C. Preferably, the composition contains 5-99.5 wt.% of a thermoplastic polymer selected from polyvinyl chloride (PVC), polystyrene (PS), poly(vinyl butyral) (PVB), 25 poly(vinyl acetate) (PVA), nylon, polyamide, polycelluloid, poly(methyl methacrylate) (PMMA), vinyl acrylic copolymer, styrene/butyl acrylic/methacrylic acid copolymer and combinations thereof.
In another aspect, the present invention pertains to a process of preparing a plastic, coating, ink, adhesive or sealant composition as described above, said process 30 comprising combining a thermoplastic polymer with an additive, said additive containing at least 5 wt.% of substituted glycoside according to the invention. In the following, further details are provided on the polymers and additives employed in such compositions.
16
Plastic compositions
In one embodiment, the invention pertains to a plastic composition comprising one or more thermoplastic polymers and an effective amount of one or more of the acylated 5 glycosides according to the invention. Within the context of the present invention, this plastic composition may refer to the shaped, consumer-ready product or to the liquid/solid base suspensions of polymer and plasticizer in the art also referred to as “plastisol”. Additionally, it may refer to polymeric “foams”, such as polyurethane foam, polyvinyl chloride (PVC) foam and Styrofoam (polystyrene). Suitable polymers 10 for use in the plastic compositions comprising one or more of the substituted glycosides according to the invention are all vinylic, cellulosic, acrylic and styrene-based polymers and co-polymers, including polyvinyl chloride (PVC), polystyrene (PS), poly(vinyl butyral) (PVB), poly(vinyl acetate) (PVA), nylon, polyamide, polycelluloid and poly(methyl methacrylate) (PMMA). The plastic compositions comprising substituted 15 glycosides according to the invention are prepared using standard processes known to the skilled person, using optional additional components that are common in the art. The plastic composition of the invention comprises from 5 to 100 wt%, preferably 10-80 wt%, more preferably 20-60 wt%, most preferably 30-50 wt%, based on the weight of the polymer, of one or more of the substituted glycosides according to the invention. 20 Expressed alternatively, the plastic compositions contain 5-100 phr (parts per hundred polymer), preferably 10-80, more preferably 20-60 phr, most preferably 30-50 phr of the glycoside plasticizer of the invention. If no other compounds than the polymer and the plasticizer are present in the composition, this corresponds to 4.76-50 wt%, preferably 9.1-44.4 wt%, more preferably 16.67-37.5, most preferably 23.1-33.3 wt%, 25 based on total weight of the composition, of one or more of the substituted glycosides according to the invention.
Preferably, the glycosides-comprising plastic composition of the invention has a glass transition temperature (Tg) lower than 80 °C, preferably lower than 50 °C, more preferably lower than 40 °C, even more preferably lower than 30 °C, most preferably 30 lower than 20 °C. In one preferred embodiment, a plastic composition comprising (PVC), polystyrene (PS), poly(vinyl butyral) (PVB), poly(vinyl acetate) (PVA), nylon, polyamide, polycelluloid or poly(methyl methacrylate) (PMMA), or mixtures thereof, 17 and from 40 phr of the substituted glycoside plasticizer of the invention has a Tg lower than 25 °C.
Ink or coating composition 5 In yet another aspect, the invention pertains to a coating composition, preferably a “latex” coating composition, comprising a synthetic resin selected from acrylic latex polymers, vinyl latex polymers, waterborne alkyds and mixtures thereof, a solvent, preferably water, as well as one or more of the substituted glycosides according to the invention.
10 Latex coating compositions, including latex resin-based inks and latex resin- based paints, cure by a process called coalescence where first the main solvent (usually water), and then the trace, or coalescing, solvent, evaporate and draw together and soften the polymeric binder particles and fuse them together into irreversibly bound networked structures, so that the paint will not redissolve in the solvent/water that 15 originally carried it. In the coating composition of the invention, the substituted glycosides act as a coalescing agent (or “coalescent”) by plasticizing the polymer particles, resulting in improved film formation upon water evaporation. It is desirable for the coalescing agent to have low water solubility, which increases its effectiveness, and have good hydrolytic stability.
20 Polymers suitable for use in the coating composition of the invention are well known in the paint art and are typically applied in the form of particles emulsified or suspended in an aqueous medium. They include, for example, the polymerization products of ethylenically unsaturated monomers, such as alkyl and alkoxy acrylates or methacrylates, vinyl esters of saturated carboxylic acids, mono-olefins, conjugated 25 dienes, optionally with one or more monomers, such as, for example, styrene, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, acrylonitrile, and vinyl chloride, as well as polyols and polyacids. Preferred coating compositions according to the invention comprise a vinyl acrylic copolymer aqueous latex emulsion or a styrene/butyl acrylic/methacrylic acid copolymer latex emulsion.
30 These polymers can have a wide range of glass transition temperatures, depending on the desired properties of the resultant coating. The polymers and coalescing agents are present in the coating compositions of the present invention in an amount that provides the desired result. Preferably, the coating composition comprises 18 one or more substituted glycosides according to the invention in an amount of at least 0.1 wt%, more preferably at least 0.5 wt-% and most preferably at least about 2 wt %, based on total weight of the coating composition. Preferably, the one or more substituted glycosides according to the invention are present in the coating composition 5 in an amount of no greater than about 50 wt%, more preferably no greater than about 25 wt% and most preferably no greater than about 10 wt% based on the total weight of the coating composition.
The coating composition of the invention may further comprise other suitable components commonly used in such compositions, including pigments, defoamers, 10 dispersing agents, adhesion promoters, antimicrobial agents etc.
The coating composition according to the invention preferably has a glass transition temperature (Tg) lower than 30 °C, more preferably lower than 25 °C, even more preferably lower than 15 °C, most preferably lower than 5 °C. In one preferred embodiment, a coating composition comprising up to 2.5 wt% of the glycoside 15 plasticizer of the invention has a Tg lower than 15 °C.
Adhesives and sealants
In a further aspect, the invention relates to an adhesive or a sealant comprising an effective amount of one or more of the substituted glycosides of the invention. Within 20 the context of the present invention, “adhesives” and “sealants” are understood to comprise all compositions comprising one or more polymeric components that are employed to adhere to or bond items together, or to fill voids in or between materials. These may be drying adhesives and sealants, including solvent based adhesives/sealants and polymer dispersion (emulsion) adhesives/sealants; pressure sensitive adhesives 25 based on e.g. (cyano)acrylates; hot-melt adhesives such as thermoplastic ethylene vinyl acetate; and multi-component glues such as acrylic polymer - polyurethane resin, which cross-link upon combination. In the art, sealants typically have lower strength and higher elongation than adhesives. As for the coating compositions of the invention, the sugar-derived plasticizer compounds of the invention serve to soften the polymer 30 particles and promote their coalescence into a homogeneous continuous film. Preferably, the adhesive or sealant composition comprises one or more substituted glycosides according to the invention in an amount of at least 0.1 wt%, more preferably at least 0.5 wt% and most preferably at least about 2 wt %, based on the total weight of 19 the adhesive or sealant composition. Preferably, the one or more substituted glycosides according to the invention are present in the adhesive or sealant composition in an amount of no greater than about 50 wt%, more preferably no greater than about 25 wt% and most preferably no greater than about 10 wt% based on the total weight of the 5 adhesive or sealant composition. The sealants and adhesives of the present invention may include conventional additives known in the art.
The adhesive or sealant composition according to the invention preferably has a glass transition temperature (Tg) lower than 30 °C, more preferably lower than 25 °C, even more preferably lower than 15 °C, most preferably lower than 5 °C. In one 10 preferred embodiment, an adhesive or sealant composition comprising up to 10 wt% of the glycoside plasticizer of the invention has a Tg lower than 15 °C.
Glass transition temperature
The liquid-glass transition temperature, or briefly “glass transition temperature”, Tg, is 15 the temperature at which the reversible transition occurs in amorphous materials from a hard and relatively brittle state into a molten or rubber-like state. A number of differing operational definitions of the glass transition temperature Tg are in use. The most frequently used definition of Tg is the temperature or temperature range associated with the energy release (ACp) peak on heating during the glass transition, as measured using 20 differential scanning calorimetry (DSC). A suitable method of determining Tg in polymer-plasticizer mixtures is provided in US2007/0282042, its contents herein incorporated by reference. Briefly, a mixture of ground PVC and plasticizer is heated from 20 to 110 °C at a heating rate of 10 °C/min, held for 3 minutes and cooled rapidly. This is repeated five times to blend the components thoroughly. Then, another run at 10 25 °C/min is performed to determine Tg. A standardized method is provided in ASTM E 1356
An alternative to DSC analysis is Thermomechanical Analysis (TMA). Another alternative is Dynamic Mechanical Thermal Analysis (DMTA), sometimes called Dynamic Mechanical Rheological Testing (DMRT), wherein Tg is characterized as the 30 temperature at which the material changes from a rigid to a flexible phase. A sinusoidal stress is applied on the material while varying the temperature and the strain in the material is measured, allowing one to determine the elastic modulus E’ and loss modulus E”. The glass transition is detected as a sudden and considerable (several 20 decades) change in the elastic modulus and an attendant peak in damping behavior tanS (E”/E’). DMTA is more informative about the material before and after the glass transition, as DMTA also measures the rubbery plateau modulus which is much more sensitive to detecting, for example, the effect of adding more plasticizer on elastic 5 modulus. Standardized test methods for thermomechanical analysis (ASTM E 1545) and dynamic mechanical analysis (ASTM E 1640) are available.
Preferably, when incorporated in amounts of between 10 and 60 wt%, preferably 20 and 40 wt% by total weight of the composition, in a polymer-comprising composition, the substituted glycosides of the invention are capable of reducing Tg of 10 said composition with at least 50 °C, more preferably at least 70 °C, even more preferably at least 80 °C, as determined using DSC or DMTA analysis.
15 21 EXAMPLES List of abbreviations
IsDEH = isosorbide-2,5-di-2-ethylhexanoate 5 ATBC = acetyl tri-n-butylcitrate DEHP = di-2-ethylhexyl phthalate DiDP = di-iso-decyl phthalate AM A = acetylated methyl- L-arabinoside AEA = acetylated ethyl-L-arabinoside 10 APA = acetylated n-propyl-L-arabinoside ABA = acetylated n-butyl-L-arabinoside AiBA = acetylated i-butyl-L-arabinoside AiPA = acetylated i-propyl-L-arabinoside AEHA = acetylated 2-ethylhexyl-L-arabinoside 15 AOA = acetylated octyl-L-arabinoside
PrEA = propionylated ethyl-L-arabinoside PrBA = propionylated n-butyl-L-arabinoside PriBA = propionylated i-butyl-L-arabinoside PriPnA = propionylated i-pentyl-L-arabinoside 20 iBEA = iso-butyrylated ethyl-L-arabinoside AEG = acetylated ethyl glycoside ester of D-galacturonic acid ABG = acetylated butyl glycoside ester of D-galacturonic acid AOG = acetylated octyl glycoside ester of D-galacturonic acid AEX = acetylated ethyl-D-xyloside 25 ABX = acetylated n-butyl-D-xyloside ABG1 = acetylated n-butyl-D-glucoside ABF = acetylated n-butyl-D-fructoside
Example 1: Synthesis and characterization of O-acvlated alkvl-arabinosides 30 1.1.1 Synthesis of O-ethyl-L-arabinoside (EA) p-TsOH (0.1 eq, 0.080 mol, 13.8 g) was suspended in ethanol (1200 ml) in an Erlenmeyer flask, and L-(+)-arabinose (120 g, 0.799 mol) was added.
22
This mixture was stirred overnight at 70 °C. After addition of another 0.025 eq p-TsOH (0.020 mol, 1.68 g), the mixture was stirred at 70 °C for 4 hours. TLC analysis (CT^CyMeOH 9:1) showed complete conversion.
The reaction mixture was cooled to room temperature. 5% NaHCCb (0.100 mol; 8.39 g; 5 167.8 ml) was added to neutralize the reaction mixture to pH 7.1. The reaction mixture was evaporated to yield a light yellow oily residue.
This residue was purified using column chromatography (silica gel 70-230 mesh, 60A, using CH2Cl2/MeOH (100/0 —» 90/10) as eluent. The product was obtained as a light yellow oil. Yield: 88.3 % (125.8 g).
10 1.1.2 Propionvlation of O-ethvl-L-ambinoside fPrEA)
The ethyl-L-arabinoside (19.6 g; 0.11 mol) obtained from Example 1.1 was stirred in pyridine (10 eq, 1.10 mol, 89 ml). Propionic anhydride (6 eq, 0.66 mol, 85 ml) was added. The mixture was stirred overnight at room temperature.
15 The reaction mixture was then poured into 1500 ml of ice water and stirred overnight at room temperature. The aqueous phase was extracted (in portions of ca. 400 ml) with EtOAc (ca. 500 ml). The organic phase was successively washed with H2O, 2N HC1 (aq), H20, 5% NaHCC>3 (aq) and H2O (all ca. 500 ml). The organic phase was dried on Na2SC>4, filtrated and evaporated. The product was obtained as a light yellow liquid, 20 which could be substantially decolored using active coal. Yield: 65.4 % (24.9 g).
1.2.1 Synthesis of n-butvl n-butvl D-galactoside uronate (O-butvl galacturonide: BG): trans glvcosidation and trans esterification with 1-octanol to (O-octvl galacturonide: OG) 25 p-TsOH (0.1 eq, 0.039 mol, 6.7 g) was suspended in 1-butanol (15 eq, 5.80 mol, 530 ml) in a 2L Erlenmeyer flask, and D-(+)-galacturonic acid.H20 (82.0 g, 0.386 mol) was added. This mixture was heated at ± 85 °C during 4 hours and stirred overnight at 60 °C. After addition of another 0.025 eq p-TsOH (0.010 mol, 1.7 g), the mixture was stirred at 85 °C for 4 hours. TLC analysis (CH2Cl2/MeOH 9:1) showed complete 30 conversion.
The reaction mixture was partly evaporated (evaporation of + 250 ml 1-butanol). Subsequently, p-TsOH (0.1 eq, 0.010 mol, 1.7 g) and 1-octanol (10 eq, 3.86 mol, 611 ml) were added. The mixture was heated to 80 °C on a rotary evaporator at 20 mbar, 23 under slow evaporation of 1-butanol. The reaction was proceeded for 6 hours at the rotary evaporator at ± 85 °C and ± 8 mbar. HPLC analysis showed almost complete conversion.
The reaction mixture was cooled to room temperature. 5% NaHCC>3 (aq) (0.125 mol; 5 4.06 g; 81.2 ml) was added to neutralize the reaction mixture to pH ±7.3. Water was pipetted off. 1-octanol was removed by vacuum distillation, T = 80 100 °C, p = ± 1- 2 mmHg, yielding an orange-red oily residue.
This residue was purified in two batches using column chromatography (silica gel 70-230 mesh, 60A, using CH2Cl2/MeOH (100/0 —> 85/15) as eluent. The product, octyl 10 octyl D-galactoside uronate was obtained as an orange oil. Yield: 80.7 % (137.4 g).
1.3.1. Synthesis of ethyl xvloside (EX) p-TsOH (0.1 eq, 0.033 mol, 5.73 g) was suspended in ethanol (10 eq, 3.33 mol, 305 ml) in a 2L Erlenmeyer flask, and D-(+)-xylose acid (50 g, 0.33 mol) was added. This 15 mixture was heated at ± 70 °C during 6 hours and stirred overnight at 60 °C. After addition of another 0.025 eq p-TsOH (0.0083 mol, 1.43 g), the mixture was stirred at 80 °C for 4 hours. TLC analysis (CHCl2/MeOH 9:1) showed complete conversion.
The reaction mixture was cooled to room temperature. 5% NaHCC>3 (aq) (0.042 mol; 3.5 g; 69.9 ml) was added to neutralize the reaction mixture to pH ±7.2. The reaction 20 mixture was evaporated to yield a light yellow oily residue.
This residue was purified using column chromatography (silica gel 70-230 mesh, 60A (± 250 g), using CH2Cl2/MeOH (100/0 —» 90/10) as eluent. The product was obtained as a light yellow oil. Yield 93.4 % (55.4 g).
25 1.3.2. Acetylation of ethyl xvloside (AEX,)
The ethyl-L-xyloside (15.9 g, 0.084 mol) obtained from Example 1.3.2 was stirred in pyridine (10 eq, 0.84 mol, 68 ml). Acetic anhydride (6 eq, 0.51 mol, 47 ml) was added. The mixture was stirred overnight at room temperature.
30 The reaction mixture was then poured into 1200 ml of ice water and stirred overnight at room temperature. The aqueous phase was extracted (in portions of ca. 400 ml) with EtOAc (ca. 500 ml). The organic phase was successively washed with H20, 2N HC1 (aq), H20, 5% NaHCC>3 (aq) and H20 (all ca. 500 ml). The organic phase was dried on 24
Na2SC>4, filtrated and evaporated. The product was obtained as a light yellow oil, which could be substantially decolored using active coal. Yield 60.0 % (15.4 g).
1.4.1. Other O-acvlated O-alkvlated monoglvcosides 5 The other O-acylated O-alkylated monoglycosides described in the Examples below were prepared using closely similar procedures, employing the analogous alkyl alcohols for the (trans)glycosidation and acid anhydrides for the acylation reactions, respectively.
10 1.4 Desree of acylation
The degree of acylation of a number of acetylated and propionylated glycosides according to the invention was determined by deacylation of a quantity of 1 gram of the compounds using a mixture of 60% iso-propanol and 40% 0.5M NaOH, followed by measurement of the amount (in wt%) of acetic acid or propionic acid liberated from the 15 saponified specimen using HPLC (Column Biorad HPX-87H, 300 x 7,8 mm, Guard column: Biorad HPX-87H, 40 mm; Pump flow 0.5 ml/min, max. pressure 1000 psi (70 bar); injection volume: 20 pi loop; detector: RI, T 35°C, eluent: 0.015 M aqueous sulphuric acid, column oven temperature: 65 °C).
20 The degree of acylation (esterification) is calculated as follows: 1. A = number of moles of acid produced from saponified specimen = wt% acid x 1000 mg/Mw acid; this equals the number of moles of H2O consumed; 2. B = number of moles of unsubstituted glycoside after saponification = weight of unsubstituted glycoside/Mw (unsubstituted glycoside) 25 = (1000 + A x Mw (H20) - A x Mw (acid produced)) / Mw (unsubstituted glycoside); 3. Degree of substitution (DS) = A/B; 4. Degree of acylation = DS / DSmax, wherein DSmax denotes the theoretical maximum degree of acylation.
30 25
Table 1: Degree of acylation of some compounds of the invention
Compound Degree of acylation ABG Ö9Ö AOG 086 ABA 088 AOA Ö72
PrEA 094
PrBA 095
PriBA 1.00 5 26
Table 2: Viscosity
Comparison between the viscosity of some acetylated and propionylated plasticizer compounds of the invention and reference compounds Texanol and acetyl tri-n-butylcitrate (ATBC), determined using an Anton-Paar Physica MCR 301 viscometer 5 equipped with a spindle of 5 cm and 2° angle.
Compound Viscosity (21 °C), mPa.s AEA 980
PrEA ÏÖ5 ABA 149Ö
PrBA 12Ö
Texanol 17 ATBC 4Ö
The plasticizers of the invention are more viscous than the reference compounds, but amply fluid for practical application.
10 27
Example 2: Thermo Gravimetric Analysis (TGA)
The volatility and temperature stability of a number of compounds of the invention was compared to a reference phthalate plasticizer (di-isodecyl phthalate (DiDP)), by using TGA (Perkin Elmer TGA-7) in the presence and absence of O2. TGA measures weight 5 loss of a material as a function of the temperature at a certain heating rate. Weight loss can be caused by evaporation or by degradation (causing formation of volatile compounds). Samples were heated from room temperature to 550 °C at a heating rate of 10 °C/min. The average sample weight was about 20 mg and measurements were performed both under air and nitrogen. Gas flows were at 40 ml/min for the balance 10 and 20 ml/min for the sample gas.
Compared to di-isodecyl phthalate (DiDP), ABG, AOG and ABA were found to display similar TGA profiles, except for showing minor amounts of water. Substantial evaporation of the substituted glycosides commences at temperatures over 200 °C. Hence, the compounds are considered to be thermally stable at processing temperatures 15 (160-200 °C).
Example 3: Preparation of dry blends
Dry blends were prepared by adding lubricant (3 phr Lankroflex ED06, Akcros), 0.25 phr stearic acid and stabilizer (2 phr liquid Ca/Zn stabilizer LZC-364, Akcros) to PVC 20 (Marvylan S7102, purchased from LVM). The plasticizers of the invention were added last in amounts of 40 and 60 phr (parts per hundred of polymer). After thorough manual mixing of the components, the mixture was heated in an oven overnight at 60 °C. After additional mixing the compound (a dry powder) was ready for processing.
25 Example 4: Compounding on a two roll mill A two roll mill (Collin Type 110P) was preheated at 166/168 °C (ffont/rear) and the slit was adjusted to 0.4 mm. The dry blend of Example 3 (80 ± 2 grams) was put on the rolls and left for half a minute. The material was mixed for two and a half minutes by cutting and kneading. After leaving the material on the rotating rolls for another half a 30 minute, the sheet was taken off.
28
Example 5: Preparation of smooth sheets: compression molding A compression press (PHI) was preheated at 160°C. A mould (sized 180 x 120 x 1 mm) was filled with about 28 grams roll milled material and covered with PET-foil and steel disks. After heating for 4 minutes at 3 tons, the pressure was raised to 20 tons for 1 5 minute followed by cooling to room temperature in 10 minutes. DMT A test strips and tensile bars for mechanical testing were cut out of the resulting sheets
Example 6: Tensile testing
Testing of mechanical properties was carried out at 20°C on a tensile testing machine 10 (Zwick Z010), equipped with a 1 kN load cell and extensometers. The pressed sheets were punched in test specimen according to ISO-37, type 2 (dumb-bells with overall length 75.0 mm, length of narrow portion 25.0 mm, width of narrow portion 4.0 mm, width of ends 12.5 mm). After clamping the test specimen, the E-modulus was determined with a test speed of 1.0 mm/min. The stress at 100% strain and the strain at 15 break were determined at 500 mm/min. (according to ISO-1184).
Table 3 displays the results of the tensile testing of PVC sheets as prepared according to Examples 3-5 using 60 phr plasticizer of the invention and DEHP, DIDP, ATBC and GRINDSTED® Soft-N-Safe (fully acetylated 1,2-hydroxystearic acid glycerol monoester, prepared by esterification of glycerol and castor oil) reference 20 plasticizers.
Table 3: Tensile data of PYC containing 60 phr plasticizer.
Plasticizer E-modulus Stress Max Strain Max (MPa) (MPa) (%) DEHP ftO IZi 167.9 DÏDP T9 13JÖ Ï41Ï "ATBC 6.0 14.9 Ï86.8 "Soft-N-Safe 6.Ï 14 A 206.9 ABG 108.6 216 169.7 AOG 4Z3 1T8 127.0 ABA 310 213 150.7 "AÖA ÏTÖ 16/9 165.2
These data demonstrate that the tensile data for R , R substituted glycoside plasticizers of the invention are slightly inferior to those of the reference compounds, but amply 25 sufficient for practical application.
29
Example 7: Glass transition temperature (T£) determination in PYC sheets using DMT A
Dynamic Mechanical Thermal Analysis (DMTA) measurements were performed using a DMTA (Rheometrics RSA-2) equipped with a film geometry. A sample (sized appr. 5 25 x 4 x 1 mm) was fixed and tested in tensile mode with frequency 1.0 Hz at 0.1% strain. A temperature scan was performed from -40°C to 150°C, at a rate of 5°C/min. Tg was chosen to correspond to maximum damping behavior tanS (E’VE’).
Table 4 displays the glass transition temperature (Tg) of PVC sheets as prepared according to Examples 3-5 using 40 and 60 phr plasticizer of the invention and DEHP, 10 DiDP, ATBC and Soft-N-Safe (Danisco) reference plasticizers.
Table 4: Glass transition temperatures (Tg) of plasticized PVC sheets determined with DMTA.
Plasticizer Tg (°C) at 40 phr Tg (°C) at 60 phr DEHP ........25 ..........“7 "DÏDP 32 ÏÏ ATBC 25 8
Soft-N-Safe 22 --------------- "ABG.................."48 TÖ AÖG.....................49 "38 "ABA .........39 33 a'OA 38 27
15 Example 8: Glass transition temperature (Tg) determination in PVC-plasticizer blends using DSC
5 mg samples of dry mixtures of ground PVC and plasticizer were placed in an aluminum DSC pan and heated from 20 to 110 °C at a heating rate of 10 °C/min using a Mettler Toledo DSC821e DSC apparatus. The samples were held for 3 minutes and 20 cooled rapidly. This was repeated five times to blend the components thoroughly. Then, another run at 10 °C/min was performed to determine Tg.
Table 5 displays the glass transition temperature (Tg) of PVC-plasticizer blends, using the plasticizer of the invention and ATBC and Texanol® reference plasticizers. Amounts are 20 wt% plasticizer based on total weight of the blend, unless indicated 25 otherwise.
30
Table 5: Glass transition temperatures (Tg) of PVC-plasticizer blends determined with Differential Scanning Calorimetry (DSC).
Plasticizer Tg (°C)
No plasticizer 90
Texanol 28. i “aTBC 28.3 “PrEA 292
PrEA 40 wt% 172
TrBA™™™”"35?ï "AEA iSk3~~~~
PriPnA 35.Ö “PriBA 2973 ABA 372 ~APA 422~™~ “ABA-A 37.4 "ABGI 444 "ABF 362 ABX 422
These data demonstrate that the R1, R2 substituted glycosides of the invention 5 are capable of reducing Tg of a PVC composition with 40 °C or more when blended in amount of 20 wt% into a PYC composition, with propionylated ethyl-L-arabinoside (PrEA) and propionylated i-butyl-L-arabinoside (PriBA) having comparable Tg reducing capacity as Texanol and ATBC.
10 Example 9: Preparation of latex compositions
Latex compositions were prepared by adding 2.5 wt%, 5 wt%, and 10 wt% (by weight of the total composition) of substituted glycosides according to the invention to water-continuous emulsions of a commercially available (AkzoNobel) vinyl acrylic copolymer and a styrene/butyl aciylate/methyl methacrylate (S/BA/MAA) copolymer. 15
Example 10: Glass transition temperature (To) determination in latex compositions using DSC
The determination of Tg in latex coating compositions comprising the plasticizers of he invention using Differential Scanning Calorimetry (DSC) was performed by scanning 31 from -15 °C to 50 °C at a rate of 10 °C/min, followed by rapid cooling and recording of a second heating run from -15 °C to 50 °C at 10 °C/min.
The results are presented in Tables 6A and 6B.
5 32
Table 6A: Glass transition temperatures (Tg) of vinyl acrylic copolymer latex compositions determined with Differential Scanning Calorimetry (DSC). The Tg of the vinyl acrylic latex compositions without plasticizer was 7.5 °C.
Tq(°C)
Plasticizer amount of plasticizer (wt% by total weight of composition) __2.5 5_ 10_
Texanol 0.4 -4.7 n.d.
ATBC 1.8 -1.0__n.d.
IsDEH 4.2 0.7 n.d.
AMA__4A__12__n.d.
AËA 4.8 11__-3.7 APA 4.1 11 n.d.
ABA 4.6 18__-2.8 ABA-A 3.6 13 n.d.
AiBA__16__2A__-14
AiPA__32__2A__n.d.
AEHA 5.1 2.7__-17
PrEA 2.5 -14 n.d.
PrBA 4.3 12 n.d.
PriBA 4.9 2.9 md._ iBEA 3.5 ~ 13 n.d.
PriPnA 2.1 -0.3 rrd._ AEG 5.7 ~ 4.3 0.5 AOG ~ 5.9__319__n.d.
AEX 4.9__310__n.d.
ABX 5.1__Z8__n.d.
ABGI__5J__T5__n.d.
ABF 6.1__57__n.d.
5 33
Table 6B: Glass transition temperatures (Tg) of styrene/BA/MMA copolymer latex compositions determined with Differential Scanning Calorimetry (DSC). The Tg of the vinyl acrylic latex compositions without plasticizer was 25.2 °C.
Tq(°C)
Plasticizer amount of plasticizer (wt% by total weight of composition) __Z5_ 5 | 10
Texanol 11.4 3.9 md._ ATBC 14.9 8.8 n.d.
IsDEH 20.9 14.0 n.d.
AMA__18J__118__n.d.
AEA 15.3__100__3.5 AEA-A__19J__135__n.d.
APA 18.2 12.7 n.d.
ABA 17.0 11.3 3.3
AiBA__135__103__3.6
AiPA 17.0__103__n.d.
AEHA 16.7 ~ 11.9 4.0
PrEA 12.3__A8__n.d.
PrBA__1A5__09__1.5
PriBA 19.6__12J__n.d.
PriPnA _164__112__n.d.
iBEA__101__102__n.d.
AEG 21.4 13.5__10.5 AOG__202__177__n.d.
AEX 22.9 18.3 n.d.
ABX 19.3 12.0 ' n.d.
ABGI 20.1 16.3__n.d.
ABF 22.0 19.9 " n.d. 1
Claims (15)
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| NL2007240A NL2007240C2 (en) | 2011-08-09 | 2011-08-09 | Sugar-based plasticizers. |
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