WO2024219965A1 - Complexe polyélectrolytique - Google Patents

Complexe polyélectrolytique Download PDF

Info

Publication number
WO2024219965A1
WO2024219965A1 PCT/NL2024/050198 NL2024050198W WO2024219965A1 WO 2024219965 A1 WO2024219965 A1 WO 2024219965A1 NL 2024050198 W NL2024050198 W NL 2024050198W WO 2024219965 A1 WO2024219965 A1 WO 2024219965A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester
anionic
cationic
water
kda
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL2024/050198
Other languages
English (en)
Inventor
Evelien MAASKANT
Willem VOGELZANG
Shanmugam THIYAGARAJAN
Julian Johannes ENGELHARDT
Evert Cornelis SIMONSZ
Louis Cornelia Patrick Maria De Smet
Wouter POST
Arijana SUŠA
Jasper VAN DER GUCHT
Johannes Teunis Zuilhof
Jacobus Van Haveren
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wageningen Universiteit
Original Assignee
Wageningen Universiteit
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wageningen Universiteit filed Critical Wageningen Universiteit
Publication of WO2024219965A1 publication Critical patent/WO2024219965A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the invention relates to a polyelectrolyte complex material.
  • the invention relates to a saloplastic material as such, more specifically a seawater- decomplexable saloplastic material, methods of making such materials, and methods of using these materials.
  • Poly electrolytes are generally soluble in water, driven by interactions between water and charge-bearing units. When two polyelectrolytes bearing opposite charges are combined together, they form a stable complex, i.e. a polyelectrolyte complex or “PEC”.
  • PEC polyelectrolyte complex
  • the standard material in the field of saloplastic PECs is a complex of poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium) (PDADMA) as polyanion and polycation, respectively. It is desired, however, to provide a greater versatility of saloplastic materials. Particularly, saloplastic PECs are sought that match better with today’s demand for more ecologically friendly plastics. This demand pertains, inter alia, to the non-biodegradable nature of PSS/PDADMA, and to the fact that this known PEC is composed of fossil-based polyolefin polymers. Accordingly, alternative saloplastic PECs are sought, and preferably non-fossil based, biodegradable, or both.
  • the invention provides, in one aspect, a polyelectrolyte complex comprising a first water-soluble polymer the repeating units of which comprise units bearing anionic groups associated with a second water- soluble polymer the repeating units of which comprise units bearing cationic groups, wherein said first and second polymers are polyesters.
  • the invention presents a method of making a polyelectrolyte complex, the method comprising: (i) providing an aqueous composition comprising a water-soluble anionic polymer comprising repeating units that are negatively charged;
  • the invention concerns a plastic formulation comprising a polyelectrolyte complex comprising a first water-soluble polymer bearing anionic groups associated with a second water-soluble polymer bearing cationic groups, wherein said first and second polymers are polyesters, and one or more additives.
  • the invention provides plastic articles made of the foregoing polyelectrolyte complex.
  • Ri and R2 each independently represent an aliphatic, cycloaliphatic, heterocyclic, or aromatic moiety, preferably selected from the group consisting of (CH2)m with m being an integer of from 2 to 6, furanylene, isohexidylene, and phenylene;
  • Rs and R4 each independently are selected from the group consisting of methyl, ethyl, propyl, butyl, and pentyl;
  • X is selected from the group consisting of F, Cl, Br, and I; M is metal, preferably Na.
  • the invention is based on the judicious insight to circumvent the necessity of using vinylic polymers as a system to create PECs and, specifically, to utilize polyesters as functional polymers.
  • polyester -based PECs can be provided that do not require salt doping in order to become plasticized.
  • anionic and cationic polymers In order for anionic and cationic polymers to be capable of forming a polyelectrolyte complex, two basic requirements apply. One is that a solvent is available with which the polymers are sufficiently miscible, preferably soluble, in order to create an environment in which the actual complexation can take place. The other is that the polymers are capable of forming a complex that can be separated from the solvent.
  • the process of the invention comprises providing an aqueous composition comprising a water-soluble anionic polyester and an aqueous composition comprising a water-soluble cationic polyester.
  • the anionic and cationic polyesters applied in the present invention will be designed such as to have a water solubility in a range of from 0.05 Mol/L to 1 Mol/L.
  • the polyesters are capable of forming a complex. I.e., upon combining the two aforementioned aqueous compositions, the anionic polyester and the cationic polyester (being dissolved in water or blended with water) will come into contact with each other, and will swiftly, possibly instantaneously, form a polyelectrolyte complex.
  • the PEC formed from the dissolved individual anionic and cationic polyesters forms a separate liquid phase, or precipitates as a solid, without a need to evaporate water.
  • the precipitate can be obtained by any technique to remove a solid from a liquid, such as by filtration.
  • said phase can be obtained using any technique to remove one separate liquid phase from the other, such as by decanting.
  • the present inventors believe that this ability to phase-separate or precipitate can be tuned by adapting either or both of the molecular weight and the charge density of the polyesters. E.g., with a sufficiently high molecular weight of the polymers, the resulting complex will precipitate from the water.
  • the skilled person is aware of factors affecting the formation, and precipitation, of a PEC. This generally relates to the ion site, charge density, polyelectrolyte concentration, pH, and ionic strength. It will be understood that polycations and polyanions having a lower charge density along their chains, will require higher molecular weights to precipitate as a PEC, than the same polymer chains having a higher density of charged groups.
  • the polymers of the present invention benefit from the effect of the electrolytic strength of a solvent, such as water, on the stability of a PEC. Accordingly, at the end of life, the PECs can be dissolved in ionic (typically NaCl or KBr) solutions, allowing the complex to be become disassociated, and thereby obtaining the corresponding polyelectrolytes.
  • ionic typically NaCl or KBr
  • polymeric articles made from the PECs of the invention when ending up in sea will quickly be falling apart.
  • the resulting separate polyelectrolytes are still polymer waste that had preferably be removed from the environment. Nonetheless, the decomplexation effectively destroys the articles as such, which considerably aids to reduce the risks for the environment.
  • the precipitated or separated phase can be liquid or solid.
  • the anionic and cationic polyesters will generally need to have a sufficient water- solubility, without themselves precipitating from water.
  • the anionic and cationic polyesters each preferably have a number-averaged molecular weight (M n ) of 1 kDa to 200 kDa, such as 2 kDa to 100 kDa, such as 5 kDa to 80 kDa, such as 10 kDa to 60 kDa, more preferably 30 kDa to 50 kDa.
  • Suitable polymers may also have a molecular weight in a range of from 7.5 kDa to 20 kDa, such as 10 kDa to 15 kDa.
  • M n is determined with Size Exclusion Chromatography.
  • the PEC by providing water, and dissolving the anionic and cationic polyesters, simultaneously, sequentially, or alternatingly. It is also conceivable to provide a solution of either of the two polyesters, cationic or anionic, and add the corresponding other polymer to such solution.
  • a solution of either of the two polyesters, cationic or anionic and add the corresponding other polymer to such solution.
  • the polymers and/or polymer solutions are generally blended with each other, so as to allow the desired complexation to occur.
  • the blending can be accomplished by mixing, stirring, or otherwise by applying any suitable technique available to the skilled person.
  • the blending will generally be done for a period of 30 seconds to 30 minutes. Shorter blending times, e.g. 5-30 seconds can be suitable as well, preferably with high-speed stirring or vigorous mixing, e.g. at more than 500 rpm. Longer blending times, e.g. 5 minutes to 1 hour or more, can be employed as well.
  • the optimal blending speeds and time to allow complexation to occur will differ also according to the scale of the production equipment and amount of loading.
  • the water in which the monomers are dissolved preferably is deionized water.
  • the anionic and cationic polyesters are blended, and preferably dissolved, generally in a concentration range, calculated on the basis of the molecular weight of a single repeating unit, of 0.01 M to 1 M, preferably 0.05 M to 0.5 M, more preferably 0.08 M to 1.0 M.
  • the anionic and the cationic polyester can be blended in a broad range of molar ratios. Generally, the molar ratio, calculated on the basis of the molecular weight of the repeating unit, is in a range of from 90:10 to 10:90, such as 20:80 to 80:20, such as 70:30 to 30:70, such as 60:40 to 40:60, such as 50:50.
  • both the anionic and the cationic repeating unit have the same number of charged groups (generally 1-3, such as 2, more typically 1).
  • the above molar ratio’s will be adapted accordingly. E.g., a ratio of 50:50 if both repeating units contain
  • the polyelectrolyte complexes are generally made by a method comprising:
  • the polyester PECs of the invention can be obtained as a phase- separated liquid or precipitated solid, with the aqueous phase from which it is formed remaining as a supernatant. This can be accomplished over time by allowing the aqueous phase to stand until phase separation or precipitation occurs. Preferably, the phase separation is further aided by centrifugation, e.g. at 2000 rpm to 6000 rpm, such as 3000 rpm to 5000 rpm, for 2 minutes to 20 minutes, such as 5 minutes to 15 minutes.
  • the PECs can generally be obtained by decanting the supernatant, or by any other suitable techniques available to the skilled person to remove a supernatant or to collect a precipitate.
  • polyester PECs of the invention are preferably subjected to dehydration, before further processing and shaping.
  • the dehydration can be done by available drying techniques.
  • a preferred method to process polyester PECs obtained as a highly viscous liquid is to spread the liquid on an inert (non-stick) sheet, e.g., a Teflon sheet, and heat in an oven or a heated press (without necessarily pressing at this stage).
  • an inert (non-stick) sheet e.g., a Teflon sheet
  • a sticky solid will result.
  • This sticky solid can be subjected to compression molding, such as hot pressing on a sheet such as above, or in a desired different mold, followed by cooling.
  • compression molding such as hot pressing on a sheet such as above, or in a desired different mold, followed by cooling.
  • the skilled person will be able for a specific polymer to determine a suitable temperature for heating.
  • equipment generally available in industrial production can be applied, such as, e.g., belt dryers, fluidized bed dryers, roller/drum dryers, trough dryers, hot air (heat-pump) dryers.
  • the skilled person will be able to simply determine its thermostability, and take this into account in choosing which dehydration technique and equipment had best be used.
  • plastic formulations can be made on the basis of compounding techniques available in the field.
  • a typical method is extrusion, and generally (as with known plastics) a variety of additives can be added for various purposes.
  • various plastic articles can be produced, generally by means of known plastic conversion routes, such as injection molding, sheet extrusion, and thermoforming.
  • the PECs of the invention are particularly suitable for foil-type applications, such as plastics used for food packaging or plastics used in the agriculture or horticulture to cover plants or soil, other packaging plastics, or, e.g., plastic shopping bags.
  • the aforementioned known vinylic PECs are saloplastics, requiring doping with salt (typically sodium chloride) in order to become sufficiently plasticized to be eligible for practical use.
  • salt typically sodium chloride
  • plasticity of the present polyester PECs can be affected by salt as well.
  • the inventors investigated these materials as saloplastics.
  • the addition of salt as a plasticizer was, in fact, unnecessary for the invented PECs.
  • the inventors believe that this effect is obtained by virtue of the comparatively larger distance between the charged groups in the polymer than in many vinyl saloplastics PECs. This reflects an essential difference between vinylic polymers and polyester polymers.
  • the polymeric backbone is determined by repeating carbon-carbon unit, with all further parts of the original vinylic monomer becoming equally repetitive side groups.
  • polyesters even with the smallest monomers, the distance between repeating groups will always include an ester group.
  • polyesters to produce saloplastics synergistically enables benefiting from the easier breaking down of ester bonds, than of the carbon-carbon bonds in vinylic polymers.
  • the size of the monomer chain between the functional groups (carboxylic or hydroxyl) will be built in into the polyester backbone. This, of course, is a known structural phenomenon of polyesters.
  • polyesters as such does not require any elucidation to the skilled person. Generally, this synthesis involves the polycondensation of a difunctional carboxylic monomer, such as a dicarboxylic acid or carboxylic derivative such as ester or acid chloride, with a diol (dihydroxyl compound).
  • a difunctional carboxylic monomer such as a dicarboxylic acid or carboxylic derivative such as ester or acid chloride
  • diol (dihydroxyl compound) diol (dihydroxyl compound).
  • the charged polyesters employed in preparing the PECs of the invention can be made generally in two ways. One is to first provide a charged diol or charged dicarboxylic monomer, and then combine it to a suitable comonomer in the polycondensation reaction.
  • the other is to first provide a non-charged polyester, and then provide the polymer with the desired charge (either cation or anion) at desired density that is suitable to form a polyelectrolyte complex.
  • the monomers should be chosen such as to have active groups that are eligible to be provided with a negative, respectively positive charge.
  • the former method is preferred.
  • the method to start from charged monomers is preferred for the anionic polyesters.
  • the direct polycondensation of charged monomers provides maximum control over the polymer architecture, and in particular the charge distribution.
  • charged polyesters having a relatively high molecular weight are preferably prepared by the post-modification of an uncharged polyester.
  • Such post-modification preferably involves the quaternarization of nitrogen, such as performed with methyl iodide or ethyl iodide.
  • Suitable chargeable groups include carbon-carbon double bonds, which can be transformed into sulfonate groups, and secondary or tertiary amines, which can be converted into ammonium groups.
  • Generally preferred charged groups are anionic SO.3 , POzf, SO.3 Na + or SO3H, and, cationic, NH4 + , NHi + X (with X being a halide, preferably Cl", Br , or I ).
  • Post-modification can also be conducted, as another preference, on the basis of click chemistry. Click reactions are known to the skilled person, a preferred example being the thiol — ene click pair.
  • providing the monomers with a thiol group will make them chargeable via reaction, after polymerization, with an alkene carrying a charged group (or an alkene that itself carries a chargeable group). Or, vice versa, providing the monomers with an alkene side-group, and after polymerization reacting this with a charged (or chargeable) molecule comprising a thiol group.
  • polyesters as the polymeric backbone for cationic and anionic polymers to be complexed into PECs, provides for a further advantage.
  • This relates to the versatility, which is greater than with vinylic polymers, in tuning the charge distribution.
  • the PECs of the invention are generally formed from polyesters made by the polycondensation of charged or chargeable dicarboxylic and dihydroxyl monomers. With this type of polymerization, it is relatively easy to build in non-charged or non-chargeable building blocks. This presents an advantageous versatility by allowing the charge distribution in either or both of the polymers to affected at will.
  • polyesters can be applied that are prepared from hydroxy acids, e.g., ferulic aid, caffeic acid, or by ring-opening polymerization of lactones such as, e.g., angelica lactones or 5-hydroxy furanone.
  • An advantage of the PECs of the present invention is that they provide a type of plastic that can be disintegrated by salt water, as this results in decomplexation of the PEC, yielding the separate anionic and cationic polyesters. This particularly holds for the preferred PECs that do not require salt doping to become plasticized. Rather, the addition of salt water will result in reducing or fully breaking down the association between the anionic and cationic polyesters that forms the complex. It will be understood that the salt-water decomplexation of the PECs of the invention is an important step in diminishing the detrimental effects of the amounts of plastics ending up in sewers and, ultimately in the sea. This phenomenon is a worldwide environmental challenge, known as the “plastic soup”.
  • the PECs of the present invention will at least be reduced to their constituent polyesters, which are not unharmful to the environment, but clearly less so than the original plastic articles.
  • polyesters are believed to be better biodegradable than vinylic polymers. This already provides for a synergistic effect with the salt-water degradation of the PEC structure. Moreover, the judicious choice of specifically using polyesters in order to produce PECs, opens up a range of possibilities to produce PECs on the basis biodegradable polymers. Accordingly, the present inventions provides the possibility of producing polymers that are biodegradable and have a desirable combination of suitable properties during both processing and use, yet combined with degradation at a sufficient rate, specifically in sea water.
  • the PECs of the present invention are made of polyesters that are made from bio-based monomers or from the substrates that can be obtained from the biomass feedstocks. This, too, presents a further synergy with the salt-based degradability of the PECs, thereby presenting an advantage that cannot be achieved with the pre-existing vinylic PECs:
  • Suitable monomers that can possibly be obtained directly or indirectly from a biological include the following:
  • (III) nitrogen containing neutral monomers with R indicating methyl, ethyl, or aryl (typically phenyl or pyridyl); or with R indicating methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tertiary butyl; these are suitable for charge to a cation at a monomer stage, or after polymerization;
  • the monomers (I-IV) are suitable to synthesize either cationic or anionic polyesters. Particularly the monomers (I-III), in combination with appropriate comonomers respectively, may be employed directly to prepare neutral polymers.
  • the “unsaturated carbon-carbon double bonds” or active “N” atoms present in the resulting polymers provide a way to introduce charge in the subsequent step to produce either cationic or anionic polyester. Alternately, the charge can be introduced in the monomer stage for the structures mentioned in I-III.
  • category (IV) represents anionic charged monomers and thus polymerizable directly resulting in an anionic polyester.
  • a skilled person may typically use the Aza-Michael addition reaction or N-alkylation reaction respectively to introduce either cationic or anionic charge in the monomer or polymer.
  • Aza-Michael addition reaction or N-alkylation reaction respectively to introduce either cationic or anionic charge in the monomer or polymer.
  • primary or secondary amine-containing sulfonic acid sodium salt can be used as a Michael donor that undergoes an addition reaction in the carbon-carbon double bond (Michael acceptor) and facilitates the introduction of the anionic group (S0.3 Na + ).
  • alkyl halide may be used to introduce the cationic charge in the “N” atom.
  • the alkyl group may vary from carbon chain length 1-10, but preferably methyl, ethyl and pentyl; halide anions vary from fluoride (F-), chloride (Cl-), bromide (Br-) and iodide (I-) but preferably (Cl-), (Br-) and iodide (I-).
  • a skilled person may alter the carbon chain length varying from 1-5 but preferably 1-3. Further, the skilled person is familiar with choosing comonomers that also play a vital role in achieving the above-said desired properties.
  • the above monomers and comonomers can be synthesized either directly or from intermediates that can be provided from biomass or other biological resources.
  • the compounds such as but not limited to phthalates/terephthalates, succinate, adipate, amino acids, amino ethanol, benzyl amine, itaconic acid, piperidine, maleic/fumaric acid, 1,4-butane diol, 1,3-propane diol, ethylene glycol, lactones, etc. are suitable to synthesize monomers for producing saloplastics.
  • the synthesis of desirable monomers can be accomplished on the basis of chemical synthesis techniques and reaction that are known to the skilled person.
  • Suitable chemical reactions include carbon-carbon direct coupling, Aza-Michael addition, A-alkylation, esterification, carbon-addition, oxidation, reduction, and sulfonation technologies.
  • catalysis this preferably is heterogeneous catalysis, as this is easier in downstream processing, and since heterogeneous catalysts have a potential to be recycled and/or reused in the subsequent runs.
  • Charged monomers can be synthesized on the basis of either or both of the dicarboxylic monomer and the dihydroxyl monomer (respectively the hydroxy acid or lactone polymer). These monomers will then be subjected to polycondensation with a preferably bio-based corresponding monomer, for which diols and diacids are commercially well available.
  • the polymeric backbone can be aliphatic, aromatic, or a combination of the two, provided that the polyesters are water-soluble.
  • the cationic polyester is all aliphatic, having a quaternized amine within the polymeric backbone.
  • An example hereof has the following repeating unit, Formula (I):
  • I- (iodide) is indicated as a negative counterion.
  • other anions are equally possible.
  • other anions that result from methylation of the nitrogen atom such as chloride or bromide, or any other anion resulting from a possible ion exchange step.
  • the anion is chloride (Ch).
  • the anionic polyester is partly aromatic, having a sulfonic acid negatively charged group.
  • An example hereof has the following repeating unit, Formula (II):
  • polyester PECs made in accordance with the invention possess mechanical properties that present an improvement over vinylic PECs. Accordingly, these polyester PECs were found to be more flexible than vinylic PEC, and to show an elongation at break that is even up to ten-fold higher than that of vinyl-based PECs.
  • the invention also pertains to a plastic formulation comprising a polyelectrolyte complex as described hereinbefore, in any of the described embodiments, and one or more additives, e.g. reinforcing fillers such as chalk or talc.
  • the invention provides plastic articles made of a polyelectrolyte complex according to the PECs presented in the present disclosure. Generally, to this end the PEC is subjected to compression forces e.g. by compression molding or by extrusion; the resulting articles can have shapes (e.g., films, fibers, rods, tapes, or tubes).
  • Dimethyl 5 -sulfoisophthalate sodium salt (100.0 g, 0.331 mol) and ethylene glycol (300.0 mL, 5.354 mol) were charged into a round bottom flask and heated to 120 °C.
  • titanium isopropoxide (2.0 mL, 0.007 mol) was added to this suspension and the suspension was heated to 195 °C (reflux temperature) under nitrogen atmosphere and continued for 3.0 h. Then the suspension was cooled down to room temperature and kept overnight in the fume hood.
  • the reaction mixture was filtered over a glass filter and ethylene glycol was removed by high vacuum distillation. The residue after distillation solidifies to a white crystalline solid. The mass was collected and finely grinded with a pestle and mortar.
  • a pre-dried 100 mL three-necked round bottom flask was equipped with a mechanical stirrer and Claisen distillation head and cooler was charged with dimethyl succinate (14.050 g, 96.139 mol), N- methyldiethanolamine (14.87 g, 124.81 mol, 1.3 equiv.) and titanium isopropoxide (27 mg, 0.1 mol%).
  • the flask was evacuated and filled with nitrogen three times.
  • the mixture was heated to 210-215 °C and stirred with 100 rpm. After 2 h the pressure was gradually decreased to 25 mbar in 30 min. After 15 min at 25 mbar, the pressure was further reduced to 0.02 mbar and the temperature was kept at 210-215 °C. After 4 h the reaction mixture was cooled to room temperature under a nitrogen atmosphere yielding a dark brown viscous liquid.
  • a round bottom flask equipped with a reflux condenser with a nitrogen inlet, and dropping funnel was charged with polymer (14.93 g) and dissolved in THF.
  • a mixture of methyl iodide (32.48 g) in THF was added dropwise. Immediately a brownish precipitates started to form.
  • the methyl iodide and THF were decanted and the polymer was washed a few times with THF.
  • the resulting brownish material was dried under reduced pressure using an oil pump (50 °C, 0.04 mbar), with a yield of 23.45 g (92%).
  • Dense PEC films were prepared by compression molding using a hydraulic press (PHI, United States of America). Rectangular or square molds were cut from a Teflon sheet ( ⁇ 120 gm thickness) with sizes varying from 1x2 cm 2 up to 4x4 cm 2 . Alternatively, a steel mold with 5x5 cm2 squares with a thickness of 550 gm was used. First, the oily PEC was dehydrated by spreading it on a Teflon sheet, and drying it in the press at 80 °C without any pressure applied for 10 min. The PEC was collected as a sticky solid. Next, the solid was charged into the Teflon/steel mold placed on top of a metal plate covered with a Teflon sheet.
  • the mold was covered with another Teflon sheet and metal plate and the whole sandwich was placed inside the hot press.
  • the PEC was heated at 80 °C for 5 min without pressure, thereafter 5 kton pressure was applied for another 5 min. Then the heating was switched off and the press was actively cooled with tap water. When the temperature in the press reached below 40 °C the pressure was released and the PEC film was removed from the mold.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des complexes polyélectrolytiques (PEC) fabriqués à partir de polyesters cationiques et anioniques solubles dans l'eau. Ces plastiques sont appropriés pour être décomposés par de l'eau de mer, et sont de préférence biodégradables. L'invention concerne également des polyesters cationiques et anioniques, et un procédé de fabrication d'un complexe polyélectrolytique.
PCT/NL2024/050198 2023-04-17 2024-04-17 Complexe polyélectrolytique Ceased WO2024219965A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23168301 2023-04-17
EP23168301.2 2023-04-17

Publications (1)

Publication Number Publication Date
WO2024219965A1 true WO2024219965A1 (fr) 2024-10-24

Family

ID=86271876

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2024/050198 Ceased WO2024219965A1 (fr) 2023-04-17 2024-04-17 Complexe polyélectrolytique

Country Status (1)

Country Link
WO (1) WO2024219965A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1367238A (en) * 1971-07-02 1974-09-18 Rhone Poulenc Sa Complex polyelectrolytes
GB1463175A (en) 1973-12-04 1977-02-02 Rhone Poulenc Sa Process for preparing complex polyelectrolytes
SU621688A1 (ru) * 1976-04-12 1978-08-30 Рубежанский филиал Ворошиловградского машиностроительного института Водорастворима полиэфирна смола в качестве пленкообразующего дл лакокрасочных покрытий и способ ее получени
WO1999032521A1 (fr) * 1997-12-19 1999-07-01 The Procter & Gamble Company Polymeres multicationiques
EP2277562A1 (fr) 2002-07-29 2011-01-26 Poly-Med Inc. Composites pour cement osseux
CN115746280A (zh) * 2022-11-11 2023-03-07 安徽皖维高新材料股份有限公司 一种水溶性聚酯及其高固含率溶液的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1367238A (en) * 1971-07-02 1974-09-18 Rhone Poulenc Sa Complex polyelectrolytes
GB1463175A (en) 1973-12-04 1977-02-02 Rhone Poulenc Sa Process for preparing complex polyelectrolytes
SU621688A1 (ru) * 1976-04-12 1978-08-30 Рубежанский филиал Ворошиловградского машиностроительного института Водорастворима полиэфирна смола в качестве пленкообразующего дл лакокрасочных покрытий и способ ее получени
WO1999032521A1 (fr) * 1997-12-19 1999-07-01 The Procter & Gamble Company Polymeres multicationiques
EP2277562A1 (fr) 2002-07-29 2011-01-26 Poly-Med Inc. Composites pour cement osseux
CN115746280A (zh) * 2022-11-11 2023-03-07 安徽皖维高新材料股份有限公司 一种水溶性聚酯及其高固含率溶液的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BIOMACROMOLECULES, vol. 10, 2009, pages 2968 - 2975
KULKARNI ET AL., ARTIFICIAL CELLS, NANOMEDICINE, AND BIOTECHNOLOGY, vol. 44, no. 7, 2016, pages 1615 - 1625
SCHAAFSCHLENOFF, ADV. MAT., vol. 27, 2015, pages 2420 - 2432

Similar Documents

Publication Publication Date Title
JP5793497B2 (ja) 生分解ポリエステル
US4789724A (en) Preparation of anhydride copolymers
Chen et al. New bio-renewable polyester with rich side amino groups from L-lysine via controlled ring-opening polymerization
JP2008075068A (ja) 樹脂組成物
EA012598B1 (ru) Сверхразветвленные полимеры, содержащие их композиции, способ их получения и их применение
CN101466763B (zh) 制备聚-l-乳酸的方法
Cao et al. Core-shell type multiarm star poly (ε-caprolactone) with high molecular weight hyperbranched polyethylenimine as core: Synthesis, characterization and encapsulation properties
JP5469748B2 (ja) 酸性イオン性液状媒体中でポリエステルを合成する方法
Zhou et al. A well-defined amphiphilic polymer co-network from precise control of the end-functional groups of linear RAFT polymers
CN110023404A (zh) 含有pbsa增塑剂的聚合物组合物
Ternat et al. Amphiphilic Multi‐Arm Star‐Block Copolymers for Encapsulation of Fragrance Molecules
WO2022143914A1 (fr) Ester d'acide gras polyhydroxy et son procédé de préparation
Matsushita et al. Conversion of sulfuric acid lignin generated during bioethanol production from lignocellulosic materials into polyesters with ɛ-caprolactone
Lee et al. Synthesis and enzymatic degradability of an aliphatic/aromatic block copolyester: poly (butylene succinate)-multi-poly (butylene terephthalate)
Perego et al. Copolymers of l‐and d, l‐lactide with 6‐caprolactone: synthesis and characterization
WO2024219965A1 (fr) Complexe polyélectrolytique
KR100365721B1 (ko) 폴리염화비닐 가소제용 고차구조제어형 지방족폴리에스테르 화합물 및 이를 포함하는 폴리염화비닐 블렌드
Chen et al. Stereocontrolled Phenol‐Yne Click Polymerization Toward High‐Performance Bioplastics with Closed‐Loop Recyclability
Ling et al. Thermoplastic elastomers based on poly (l‐Lysine)‐Poly (ε‐Caprolactone) multi‐block copolymers
JP2024517602A (ja) ポリプロピオラクトン及びその調製方法
NL2015266B1 (en) Poly(alkylene furandicarboxylate)-comprising polyester.
JPWO2009087910A1 (ja) 生分解性ポリマーの製造方法
WO2025045937A1 (fr) Polymère de polyesteramide
Abid et al. Preparation of new poly (ester triazole) and poly (amide triazole) by “click chemistry”
Celli et al. Polymers from monomers derived from biomass

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24722091

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 24722091

Country of ref document: EP

Kind code of ref document: A1