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WO2018186744A1 - Synthèse et utilisation de polyesters linéaires à base de glucides - Google Patents

Synthèse et utilisation de polyesters linéaires à base de glucides Download PDF

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Publication number
WO2018186744A1
WO2018186744A1 PCT/NL2018/050211 NL2018050211W WO2018186744A1 WO 2018186744 A1 WO2018186744 A1 WO 2018186744A1 NL 2018050211 W NL2018050211 W NL 2018050211W WO 2018186744 A1 WO2018186744 A1 WO 2018186744A1
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Prior art keywords
linear
acid
based polyester
galx
carbohydrate
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Ceased
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PCT/NL2018/050211
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English (en)
Inventor
Francesco PICCHIONI
Ionela GAVRILA
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Rijksuniversiteit Groningen
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Rijksuniversiteit Groningen
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes

Definitions

  • the invention relates to the field of polymer chemistry, more in particular to the synthesis of novel biobased linear polymers and their applications, among others as rheology modifiers or thickeners in
  • Additives have long been used in coating compositions for various purposes.
  • viscosity control agents, surfactants, sag-control agents, anti-foaming agents and other materials are added to coating compositions in minor amounts for their respective functions.
  • Rheology modifiers are also added to such compositions not only for increasing the viscosity of the coating compositions but to maintain the viscosity at desired levels under varying process conditions and end-use situations. Secondary effects obtained from the rheology modifiers include protective colloidal action, improvement in pigment suspension, leveling and flow. Some of these properties are also desired in similar type compositions, for instance textile treating compositions, cosmetics, paper compositions, well drilling, firefighting foams, detergents, pharmaceuticals, agricultural formulations, and emulsions of all kinds. It can be seen rheology modifiers are used in a variety of compositions.
  • rheology modifiers While the discussion of the reaction products which follows is with reference to them as “rheology modifiers”, it should be understood this term is used broadly. That is, “rheology modifiers” as used herein is meant to encompass such terms as thickening agents, thixotropic agents, viscosity modifiers and gelling agents.
  • rheology modifiers are bio-based or synthetic polymers. Natural products such as the alginates, casein, and gum tragacanth and modified natural products such as functionalised cellulose, gums (xanthan, guar), proteins (collagen) etc. are useful rheology modifiers. These mostly contribute due to their hydrodynamic volume and
  • rheology modifiers are used with varying degrees of success.
  • Synthetic rheology modifiers have also been used. These materials include the carboxyvinyl ether copolymers, acrylic polymers and maleic anhydride/styrene copolymers.
  • the known rheology modifiers have various deficiencies.
  • the natural rheology modifiers are susceptible to biological attack. Synthetic rheology modifiers are not subject to such attack yet most of them do suffer from having less than desirable thickening qualities over a wide range of end uses and/or film forming concentrations.
  • thickeners which rely on (macro)molecular structure factors
  • -thickeners which have as characteristic a dual hydrophilic- hydrophobic type of structure and where the hydrophobic groups tend to cluster both at intra- and inter-molecular level, causing an increase in viscosity of the polymer solution.
  • the resulting novel (shear) thickener linear sugar based polyesters have the potential of addressing various water-based applications by way of controlled hydrophilicity of sugar based polyesters by varying the degree of deprotection and/or size/type/ configuration of one of the co-monomers.
  • the invention also provides a thickener for rheological systems where it is required in order to increase the viscosity and/or stabilise the suspension, emulsion media.
  • This can be used for paints and coatings but also for cosmetic/detergent emulsion systems.
  • the invention relates to a method for providing a linear carbohydrate-based polyester, comprising the steps of:
  • X is H or a linear aliphatic moiety, preferably a linear C 1 -
  • R and R' are linear alkyl chains, more preferably C 1 -C 3 alkyl; with a diol in the presence of a suitable catalyst to obtain a Galx -based polyester; and (ii) subjecting said Galx-based polyester to a hydrolytic deacetalisation reaction to convert at least part of the diacetal moieties to dihydroxide moieties.
  • X is a linear C 1 -C5 alkyl; and/or R and R' are C 1 -C3 alkyl chains.
  • said bicyclic acetalized galactaric acid derivative is dimethyl- 2,3:4,5-di-0-isopropylidene-galactarate (Galxl)
  • the diol is preferably of the general formula wherein is a linear or cyclic ahphatic hydrophobic (e.g. cycloalkyl, aryl) unit.
  • the diol is selected from the group consisting of linear ahphatic ⁇ , ⁇ -diols, such as 1,3-propanediol, 1.4- butanediol, 1,5-pentanediol, 1,6-hexanediol. or 2 , 3 : 4.5 - di-O-isopropylidene - galactitol or 2.3 : 4.5 - di-O-methylene-galactitol .
  • Exemplary homopolyesters that may be provided in step (i) of a method of the invention include the following Galx 1-1, 3 propanediol and Galx1- 2,3:4,5-di-0-isopropylidene-galactitol homopolyesters:
  • Step (i) of a method according to the invention may comprise reacting the bicyclic acetalized galactaric acid derivative and the alcohol in the presence of one or more further co-monomer(s).
  • the further monomer comprises a cross-linking moiety, such as an ⁇ , ⁇ -unsaturated functionality.
  • the further co-monomer is itaconic acid or ester thereof, such as dimethylitaconate or dibutylitaconate.
  • the itaconic acid is preferably obtained from a renewable source. For example, it can be produced on an industrial scale via ferment ation with Aspergillus terreus with a production intensity of 80 g L-l. (T. Willke and K. D. Vorlop, Appl. Microbiol.
  • Suitable catalysts for use in a method of the invention include dibutyltin oxide (DBTO) and other organometallic catalyst which act as Lewis acids, such as Ti alkoxides; Sb, Ge, Sn oxides; Zn, Mn, Ca, Co, Cd acetate.
  • DBTO dibutyltin oxide
  • organometallic catalyst which act as Lewis acids, such as Ti alkoxides; Sb, Ge, Sn oxides; Zn, Mn, Ca, Co, Cd acetate.
  • step (ii) of a method of the invention the Galx -based polyester is subjected to a deprotection reaction wherein at least part of the diacetal moieties are hydrolyzed to dihydroxide moieties.
  • this is performed by dissolving the Galx-based polyester in an (aqueous) acid solution and incubating at room temperature to obtain the desired degree of deacetalisation. See Scheme 1 below.
  • the Galx-based polyester is purified, e.g. to remove catalyst, and dried prior to dissolving it in an acid solution.
  • the solution of acid is a aqueous solution of sulfuric acid, hydrochloric acid, Amberlyst 15, p-toluene sulfonic acid, acetic acid, trifluoroacetic acid, more preferably formic acid.
  • a formic acid solution in chloroform preferably 88% volumetric, is used.
  • the cleprotection (deacetalisation) reaction can be performed up to the desired degree of hydrolysis is achieved. In one embodiment, it comprises incubating up to 4 hours, preferably up to 3 hours, more preferably up to 2 hours. Good results are obtained wherein step (ii) comprises incubating during a time period of 15 to 180 minutes, preferably 20 to 150 minutes, more preferably 30 to 120 minutes.
  • the deprotection reaction is not performed to completion such that the resulting polyester still comprises diacetal moieties.
  • At least 20%, preferably at least 30%, more preferably at least 50% of the diacetal moieties are converted to dihydroxide moieties. In one embodiment, up to 95%, 90% or 85% of the initial protecting groups is hydrolyzed.
  • the diacetal moieties are hydrolyzed into dihydroxide moieties, thus leaving a significant amount of the Galx-residues in the polymer still in the acetahzed form.
  • at least 3%, preferably at least 5%, like 7, 8, 9, or 10%) of the Galx-residues in the final linear polymer is still in the acetalized form. See also Example 3 showing that the degree of hydrolytic deacetalisation can be controlled, which is advantageously used to steer the (surface active) properties of the polymer. See Figure 7.
  • the Galx-based polyester comprising dihydroxide moieties obtained may be precipitated, washed and dried.
  • the invention also provides a linear Galx-based polyester obtainable by a method according to the invention.
  • the carbohydrate-based polyester can have the numerical average molecular weight between 6000 and 30000 g/mol.
  • the invention provides a fully deprotected linear carbohydrate-based polyester of the general formula
  • R and R' are C 1 -C 3 alkyl, and wherein the remaining Acn groups are H.
  • 40-60% , 50-80% or 60-90%, of the Acn- groups are H.
  • the polyester may be of the formula
  • a linear Galx -based polyester provided in the present invention is not taught or suggested in the prior art.
  • US 3,083,187 describes polyesters with a polymeric backbone constructed by reacting ahphatic or aromatic dibasic acids (A) with aliphatic diols (B).
  • the polymeric backbone is substituted with polyalkyleneglycols, i.e. the polyalkyleneglycols are not part of the polymeric backbone.
  • the polymeric backbone is substituted with monoalkylethers of polyalkyleneglycols using two methods. In the first method, the substitution is established by reacting such polyalkylene glycols with reactive centers in the polymeric backbone: the hydroxyl groups of dibasic acids of e.g. mucic acid.
  • [9]) discloses carbohydrate-based polyesters made from bicyclic acetalized galactaric acid. Unlike the present invention, the polyesters are fully protected by acetal groups. Lavilla et al. is completely silent about converting at least part of the acetal groups to hydroxides.
  • a hnear (partially) deacetalised Galx -based polyester as provided herein has unique properties, and is advantageously used as rheology modifier or thickener.
  • an emvdsion composition comprising a linear (partially) deacetahsed Galx-based polyester according to the invention.
  • said composition is a cosmetic or detergent composition, an adhesive, coating or paint composition
  • Figure 3. (A) Conversion deacetalisation A-GlG2ol-62 polyester in HCOOH 88% as function of the reaction time. (B) the degree of acetal removal can be controlled by adjusting the concentration of the used aqueous acid, hydrolytic removal of the acetal group by using a solution of trifluoro acetic acid (TFA). Two samples of 200 mg of dry and catalyst -free A-GlGlol-64 polyester were dissolved in a volume of 1ml TFA 65% solution in water, respectively in 1ml TFA 90% solution in water.
  • TFA trifluoro acetic acid
  • Figure 9 Overview surface tension as function of concentration of fully and partially deprotected G1PD-58 and GlGlol-64 samples in water.
  • the NMR spectra were recorded using a Varian Mercury Plus equipment operating at 400MHz. Approximately 10 respectively, 50mg of sample were dissolved in 1 niL of deuterated solvent for 1H NMR and 13C NMR. A total of 64 scans were acquired for the 1H and 5000 for the 13C spectra, with a relaxation delay of Is.
  • the FTIR spectra were recorded with a Shimaclzu IR Tracer 100 equipped with an ATR accessory (diamond crystal, Graseby Specac), using a Happ- Genzel apodisation.
  • ATR accessory diamond crystal, Graseby Specac
  • the average molecular weight and polydispersity of the polymer samples prior to the deprotection reaction were determined using a Viscotek Gel Permeation Chromatography system. Chloroform was used as mobile phase and the molecular weight values of the samples were determined based on a universal calibration method. For calibration, polystyrene standards were used. Rheological characterization of the poly(galactaric ester) samples in water
  • the rheological measurements were performed with a Thermo Fisher Scientific Haake Mars III rheometer. A volume of 2 ml of poly(galactaric esters) in water was placed in the cone-plate unit and the viscosity response was measured as function of a shear rate increasing from 0.1 to 1750 s -1 . The surface tension of the polymer solutions was determined with a
  • This example describes an exemplary general protocol for synthesising the acetalized poly(galactaric esters).
  • the average molecular weight of the obtained polyesters can be adjusted by increasing the reaction time. Since no solvent is used during the reaction time.
  • Example 1A An equimolar mixture of dimethyl-2,3:4,5-di-0-isopropylidene-galactarate (Galxl) and 2,3: 4,5-di-O-isopropylidene-galactitol (Galxlol) together with an amount corresponding to 0.4%mol (to the monomers) of DBTO, were brought into a 3-neck cylindrical flask equipped with a magnetic coupling stirrer, a nitrogen gas inlet and a temperature controlled distillation setup. The temperature of the reaction was set to 142°C (temperature of the oil bath) and a 250 ml/min nitrogen flow was set during the first stage of the reaction (3.5 hours).
  • Table 1.1 herein below provides an overview of exemplary acetahzed poly(galactaric esters).
  • Example IB This example describes a method wherein a bicychc acetalized galactaric acid derivative and alcohol are reacted in the presence of a co-monomer comprising a cross-linking moiety.
  • DMI dimethyl itaconate
  • the resulting acetalized co-poly(galactaric ester) product is dissolved in chloroform and precipitated in diethyl ether.
  • the polymer powder is recovered by vacuum filtration and it is dried of solvent until constant weight in the vacuum oven.
  • Table 1.2 Overview exemplary acetalized co-poly (galactaric esters).
  • This example describes the general deacetalisation procedure of a method according to the invention.
  • the hydrolytic deprotection of the acetal group can be performed b using an aqueous acid solution.
  • a sample of purified and vacuum dried acetalised poly(galactaric ester) is dissolved in the aqueous acid solution and kept at room temperature.
  • concentration and the reaction time are chosen depending on the desired degree of deacetalisation (see examples below).
  • the polymer solution is precipitated and washed several times with a cold non-solvent, mostly diethyl ether.
  • the recovered product is dried in the vacuum oven until constant weight.
  • acids for the acetal removal reaction are: sulfuric acid, hydrochloric acid, para-toluene sulfonic acid, acetic acid, formic acid, trifluoracetic acid etc.
  • acids for the acetal removal reaction include strongly acidic resins of the styrene-divinylbenzene type, e.g. sold, inter alia, under the trade name Amberlyst 15. Formic acid and trifluoracetic acid are preferred.
  • the hydrolytic removal of the acetal group was performed using a solution of formic acid (HCOOH). 20 mg of dry and catalyst-free A-GlG2ol-62 polyester sample was dissolved in a volume of 1 ml HCOOH 88% solution in chloroform and with 2% water. The resulted polymer solution was kept at room temperature and samples were taken after 0.5, 1, 2, 4 respectively 5 hours. The sampled polymer was precipit ated and washed several times with cold diethyl ether. The recovered products were dried in the vacuum oven until constant weight.
  • HCOOH formic acid
  • Figure 1 shows the FTIR analysis comparison before and after
  • Example 2B A sample of 200 mg dry and catalyst free A-IGlGlol-MP3 polyester was dissolved in 1 ml TFA solution 90% vol. and kept at room temperature reacting for 30 minutes. Subsequently, the polymer solution was
  • step (ii) of a method of the invention can be controlled in order to accommodate for specific properties of the resulting polymer. i) By adjusting the deacetalisation reaction time
  • Figure 2 shows an overlay 1H NMR spectra of A-GlG2ol-62 polyester sample before deacetalisation and after 0.5 hours, 1 hour, 2 hours, 4 hours and 5 hours of incubation at room temperature, respectively.
  • the hydrolytic removal of the acetal group is suitably performed by using a solution of trifluoroacetic acid (TFA).
  • TFA trifluoroacetic acid
  • Two samples of 200 mg of dry and catalyst-free A-GlGlol-64 polyester were dissolved in a volume of 1ml TFA 65% solution in water, respectively in 1ml TFA 90% solution in water.
  • the resulted polymer solutions were kept at room temperature for 0.5 hours. Subsequently the polymer was precipitated and washed several times with cold diethyl ether.
  • the recovered products were dried in the vacuum oven until constant weight.
  • the degree of acetal removal can also be controlled by adjusting the concentration of the used aqueous acid.
  • This example demonstrates the added value of these novel poly(galactaric esters) by showing their rheological and surface tension in water as response to the change of different parameters.
  • the poly(galactaric esters) can be dissolved or suspended in water. Since the molecular weight of the polymers is in the 10 3 - 10 4 g/mol region, no (or up to a low extent) associative behaviour due to chain entanglements is expected to happen. More likely, strong intermolecular interactions such as hydrogen bonding between the free OH groups and the water molecules along with hydrophobic strong associations between the internal non-polar units are the ones assumed to give the thickener response of the polyester samples in an aqueous system.
  • the water-polyester system shows relatively good stabihty in the room temperature domain with a gradual decrease in viscosity when increasing the temperature.
  • Figure 4 shows the thickening effect of the exemplary poly(galactaric ester) G1PD-58 (10 wt% in water) as a function of
  • the response to the steadily increasing shear rate is a high viscosity in the low shear rate range (0.01-1 s -1 ) with a lower viscosity in the intermediate and high shear rate region (1-1000 s -1 ).
  • This type of behaviour is characteristic to a pseudoplastic or shear-thinning fluid.
  • Figure 5 illustrates the dependence on the concentration of polymer in the water solution/ dispersion. Shown is the viscosity as function of shear rate measured for GlPD-58 in water at 2.5wt%, 5wt.% and 10wt.%. Surprisingly, by increasing the concentration of the polymer, a higher viscosity response is obtained while maintaining the shear thinning behaviour.
  • Figure 6 illustrates the dependence on the type of co-monomer (type of hydrophobic unit). Shown is the viscosity as function of shear rate measured for (panel A) GlPD-58, GlG2ol-62 at a concentration of 2wt.% in water; and (panel B) for GlPD-58 and GlGlol-64 4wt.% in water. The strength of the formed hydrophobic clusters and therefore the
  • an alkyl unit can contribute to stronger associative interactions than a cyclic structure.
  • Figure 7 illustrates the dependence of the shear thinning behaviour on the degree of deacetalisation. Shown is the viscosity as a function of shear rate measured for GlGlol-64 samples partially (30%) and fully acetal
  • the poly(galactaric esters) show a better solubility in water at pH > 7 (concentration dependent). There is little influence on the rheological profile of the solution as shown in figure 8. However, with respect to practical applications of the polymer and from the compounding point of view, an increased solubihty will also reduce the possibility of the polymer
  • EXAMPLE 5 Surfactant activity Figure 9 shows the surface tension as a function of the concentration of exemplary polyesters GlPD-58 and GlGlol-64 samples in water. Even in the dilute concentration region (up to 4wt.%) the surface tension of the water can be decreased by adding the hydrophilic poly(galactaric esters). The figure also shows the surface tension of partly deprotected Galx polyesters. Dispersions of 4wt.% GlPD-58 and GlGlol-64 (30% deprotected) in demineralised water were prepared. The determined surface tension values are comparable with the ones obtained for the fully deacetalised homologues polyesters at 1.5wt% concentration in water. REFERENCES
  • homopoliesteres y copoliesteres aroniaticos y alifaticos a Portugal de derivados de alditoles y acidos aldaricos diacetalizados, asi como homopoliesteres y copoliesteres aroniaticos y alifaticos obtenidos de dicho proceedimiento. Spain: Universitat Politecnica de Catalunya.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne le domaine de la chimie des polymères, plus particulièrement la synthèse de nouveaux polymères linéaires d'origine biologique et leurs applications, entre autres en tant que modificateurs de rhéologie ou épaississants dans des formulations aqueuses. La présente invention concerne un procédé de fourniture d'un polyester linéaire à base de glucides, comprenant (i) la réaction d'un dérivé d'acide galactarique acétalisé bicyclique (Galx) avec un diol en présence d'un catalyseur adapté pour obtenir un polyester à base de Galx ; et (ii) la soumission dudit polyester à base de Galx à une réaction de désacétalisation hydrolytique pour convertir au moins une partie des fragments diacétal en fragments hydroxyde.
PCT/NL2018/050211 2017-04-05 2018-04-05 Synthèse et utilisation de polyesters linéaires à base de glucides Ceased WO2018186744A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3083187A (en) 1959-06-22 1963-03-26 California Research Corp Detergent polyesters
FR3024733A1 (fr) * 2014-08-05 2016-02-12 Coatex Sas Agent epaississant pour systemes aqueux, formulations le contenant et utilisations.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3083187A (en) 1959-06-22 1963-03-26 California Research Corp Detergent polyesters
FR3024733A1 (fr) * 2014-08-05 2016-02-12 Coatex Sas Agent epaississant pour systemes aqueux, formulations le contenant et utilisations.

Non-Patent Citations (14)

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Title
"Comprehensive Polymer Science: the synthesis, characterization & applications of polymers", 1989, PERGAMON PRESS, pages: 14 - 15,290-291
"Handbook of Green Chemistry", 2014, JOHN WILEY & SONS LTD, article "Green Processes, Designing Safer Chemicals"
"Synthetic Methods in Step-Growth Polymers", 2003, JOHN WILEY & SONS LTD, pages: 72 - 73
BARMAR M; BARIKANI M; KAFFASHI B: "Synthesis of Ethoxylated Urethane and Modification with Cetyl Alcohol as Thickener", IRAN POLYM J, vol. 10, 2001, pages 331 - 5
CHASSENIEUX C; NICOLAI T; BENYAHIA L: "Rheology of associative polymer solutions", CURR OPIN COLLOID INTERFACE SCI, vol. 16, 2011, pages 18 - 26
DATABASE COMPENDEX [online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; 11 July 2011 (2011-07-11), LAVILLA C ET AL: "Carbohydrate-based polyesters made from bicyclic acetalized galactaric acid", XP002773535, Database accession no. E20112914149949 *
GLASS JE: "A perspective on the history of and current research in surfactant-modified, water-soluble polymers", JCT, J COATINGS TECHNOL, vol. 73, 2001, pages 79 - 98
KELSEY, D. R.; SCARDINO, B. M.; GREBOWICZ, J. S.; CHUAH, H. H.: "High impact, amorphous terephthalate copolyesters of rigid 2,2,4,4-tetramethyl-1,3-cyclobutanediol with flexible diols", MACROMOLECULES, vol. 33, no. 16, 2000, pages 5810 - 5818, XP009070430, Retrieved from the Internet <URL:http://doi.org/10.1021/ma000223> DOI: doi:10.1021/ma000223+
LAVILLA C ET AL: "Carbohydrate-based polyesters made from bicyclic acetalized galactaric acid", BIOMACROMOLECULES, vol. 12, no. 7, 11 July 2011 (2011-07-11), AMERICAN CHEMICAL SOCIETY USA, pages 2642 - 2652, XP002773794, DOI: 10.1021/bm200445w *
LAVILLA ET AL., BIOMACROMOLECULES, vol. 12, no. 7, 2011, pages 2642 - 2652
LAVILLA, C.; ALIA, A; DE ILARDUYA, A M.; BENITO, E.; GARCIA-MARTIN, M. G.; GALBIS, J. A; MUNOZ-GUERRA, S., CARBOHYDRATE-BASED POLYESTERS MADE FROM BICYCLIC ACETALIZED GALACTARIC ACID. BIOMACROMOLECULES, vol. 12, no. 7, 2011, pages 2642 - 52, Retrieved from the Internet <URL:http://doi.org/10.1021/bm200445w>
MUNOZ GUERRA, S.; LAVILLA AGUILAR, C.: "Sintesis de homopoliesteres y copoliesteres aromaticos y alifaticos a partir de derivados de alditoles y acidos aldaricos diacetalizados, asi como homopoliesteres y copoliesteres aromaticos y alifaticos obtenidos de dicho procedimiento", 2013, UNIVERSITAT POLITECNICA DE CATALUNYA
T. WILLKE; K. D. VORLOP, APPL. MICROBIOL. BIOTECHNOL., vol. 56, 2001, pages 289 - 295
WINNIK MA; YEKTA A: "Associative polymers in aqueous solution", CURR OPIN COLLOID INTERFACE SCI, vol. 2, 1997, pages 424 - 36, XP027090889

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