EP4267633A1 - Polymères à faible dispersité obtenus par amorçage à la lumière infrarouge proche et au moyen d'un catalyseur au fer - Google Patents

Polymères à faible dispersité obtenus par amorçage à la lumière infrarouge proche et au moyen d'un catalyseur au fer

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Publication number
EP4267633A1
EP4267633A1 EP21843905.7A EP21843905A EP4267633A1 EP 4267633 A1 EP4267633 A1 EP 4267633A1 EP 21843905 A EP21843905 A EP 21843905A EP 4267633 A1 EP4267633 A1 EP 4267633A1
Authority
EP
European Patent Office
Prior art keywords
providing
polymers
iron
range
atrp
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.)
Withdrawn
Application number
EP21843905.7A
Other languages
German (de)
English (en)
Inventor
Bernd Strehmel
Veronika Strehmel
Ceren Kütahya
Nicolai Meckbach
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.)
Phosuma Photonic & Sustainable Materials GmbH
Original Assignee
Phosuma Photonic & Sustainable Materials GmbH
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 Phosuma Photonic & Sustainable Materials GmbH filed Critical Phosuma Photonic & Sustainable Materials GmbH
Publication of EP4267633A1 publication Critical patent/EP4267633A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Definitions

  • the invention is in the field of polymer chemistry and relates to polymers with low dispersity and block copolymers and polymeric networks obtainable therefrom.
  • the initiating radical then adds to a monomer and initiates chain growth, with chain growth being deactivated by reaction of the macroradical with the transition metal complex and halide, with the transition metal complex being in the higher oxidation state than the activator and alkyl halide, which in this case is the task of a macroinitiator takes over to regenerate as a dormant species. Controlling this equilibrium ensures a low concentration of radicals, minimizes the unwanted radical terminations corresponding to free radical polymerization such as recombination and disproportionation, and allows the polymerization to proceed in a controlled manner by growing essentially all chains simultaneously, resulting in a low dispersity (£>) expresses.
  • MMA is polymerized in MeCN in the presence of ethyl bromophenyl acetate (EBPA) as an ATRP starter and FeCh.
  • EBPA ethyl bromophenyl acetate
  • US 6,140,384 (FUJI) relates to photopolymerizable compositions comprising an addition polymerizable compound having an ethylenically unsaturated double bond, a sensitizing cyanine and a titanocene compound.
  • the controlled synthesis of polymers does not take place according to a living radical polymerization mechanism.
  • the object of the present invention was therefore to provide polymers or block copolymers and networks of these substances based on monomers, which are characterized by low dispersity and are formed according to a living controlled radical polymerization mechanism.
  • the production should also provide polymers with a tailor-made molecular weight and be as environmentally friendly as possible, i.e. without the use of heavy metal ions with a negative impact on human metabolism and with the lowest possible energy light, in order to enable the synthesis of versatile materials that also work in the UV and visible spectral range absorb.
  • step (g) irradiating the mixture from step (f) with a NIR source emitting light in the range of about 700 to about 1200 nm.
  • step (g) irradiating the mixture from step (f) with a NIR source emitting light in the range of about 700 to about 1200 nm.
  • the photoinduced atom transfer-based free-radical polymerization in the presence of alkyl bromides and iron(II) compounds leads for the first time to corresponding polymers of the desired low dispersity if an NIR sensitizer containing a barbituric acid group is preferably used.
  • an NIR sensitizer containing a barbituric acid group is preferably used.
  • the sensitizers mentioned it is also possible to trigger the radical chain reaction using long-wave NIR radiation, which energy-saving LEDs can emit in the near infrared (NIR).
  • the copper compounds previously regarded as obligatory could be replaced by iron compounds, which are significantly less critical from a toxicological point of view.
  • the polymers can be in terms of their molecular weight synthesize with pinpoint accuracy and can further react to form block copolymers and networks with a very uniform network arc spacing
  • the suitable monomers includes the large group of mono- or polyolefinically unsaturated hydrocarbons, ie above all alkenes, dienes and correspondingly unsaturated carboxylic acids and carboxylic acid esters. Above all, acrylic acid, methacrylic acid, maleic acid and their esters with C1-C4 alcohols should be mentioned here. It is also conceivable to use olefinically unsaturated monomers that have functional groups and thus produce (block) copolymers that have special properties, for example absorbing UV or visible light and can be used as a starting material for photostable plastics, as cosmetic light protection filters or Encapsulation material suitable for light-sensitive active ingredients.
  • the cyanines In the ATRP reaction, the cyanines have the function of a sensitizer for the absorption of NIR radiation, with which the radical chain reaction is started. Accordingly, it makes sense to use substances that absorb in the same range, i.e. from around 700 to around 2,100 nm. Chemically, these are derivatives of barbituric acid, the preferred species being characterized by having a heptamethine structure:
  • the two structural elements are coupled by elimination of HCL.
  • the particularly preferred cyanines are represented by the following structures (1) to (5):
  • alkyl bromides are suitable as dormant species in the AT RP process, it has been found that the best results are obtained using alkyl bromides.
  • the definition of alkyl bromides is to be understood broadly: in addition to the C1-C10 alkyl halides such as butyl bromide, hexyl bromide or octyl bromide, species that are present as quaternary ammonium salts, such as the tetraalkylammonium bromides and in particular tetrabutylammonium bromide, are also particularly suitable.
  • iron(III) compounds in addition to the C1-C10 alkyl halides such as butyl bromide, hexyl bromide or octyl bromide, species that are present as quaternary ammonium salts, such as the tetraalkylammonium bromides and in particular tetrabutylammonium bromide, are also particularly suitable
  • iron(III) bromide occupies a preferred position.
  • iron(III) compounds together require a complex-forming ligand such as amines, phosphines or halides. This simplifies the design of the ATRP system with NIR light, whereby problematic compounds such as amines can be dispensed with.
  • Solvents such as acetonitrile and in particular N,N-dimethylformamide are particularly suitable for this purpose.
  • the polymerization can also be carried out in water as a green solvent.
  • TMPP tris-(4-methoxyphenyl)phosphine
  • ATRP procedure The polymerization is carried out in the manner known from the prior art. In particular reference is made to the publication by X. Pan et al, MACROMOL RAPID COMMUN. 38, p. 1600651 (2017) and S. Dadashi-Silab et. al., CHEMICAL REVIEWS 116, 10212-10275 (2016). referred.
  • the components are placed in a photoreactor, with about 0.005 to about 0.5 parts and preferably about 0.01 to about 0.1 parts each of the other components—ie cyanine dye/sensitizer, alkyl bromide—for 100 parts of the monomer or monomer mixture , iron(III) compound and, if appropriate, ATRP starter - are omitted.
  • the mixture is then dissolved in a solvent, for example acetonitrile, but preferably DMF, homogenized and degassed.
  • the reaction mixtures are then exposed to NIR radiation using four NIR LEDs (approx. 790 nm), which are arranged around the photoreactor at an angle of 90° between each LED and a distance of 10 to 15 mm.
  • the light intensity of each LED should be about 100 mW • cm 2 within the illuminated area at the middle height on the surface of the tube.
  • the photoreactor is then sealed in a light-tight box, the mixture is cooled with air and stirred with a magnetic stirrer during irradiation.
  • this method of the polymers according to the invention or their products can be used for the production of paint additives.
  • the reactor was charged with EBPA (136.3 mg, 0.560 mmol), FeBrs (6.6 mg, 22.3 pmol), TBABr as a ligand (7.2 mg, 22.3 pmol) and the sensitizer in in this case Sensl (164.4 mg, 0.22 mmol).
  • Sensl 164.4 mg, 0.22 mmol
  • destabilized MMA 5.64 g, 564.7 mol
  • DMF solvent
  • the resulting polymers were precipitated in methanol and then dried under reduced pressure. Repeated absorption in THF and renewed precipitation with subsequent drying in a vacuum drying cabinet ultimately provided the polymer with the required purity, with the NMR spectra showing no recognizable amounts of residual solvent.
  • Figure 4/5 UV-Vis spectra of the mixture from Example 1 in Table 1 without FeBrs (solid line) and with FeBrs (dashed line);
  • Figure 5/5 GPC of the polymers from Examples 19 and 20, which was produced under aerobic conditions;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des polymères ayant une dispersité inférieure à 1,4, qui sont obtenus par exposition d'un mélange composé de monomères polymérisables par voie radicalaire, de cyanines en tant que sensibilisateurs, de composés de fer(III), de bromures d'alkyle et, éventuellement, d'amorceurs de polymérisation radicalaire par transfert d'atome (ATRP), à une source NIR qui émet de la lumière dans une plage allant d'environ 700 à environ 1 200 nm.
EP21843905.7A 2020-12-22 2021-12-20 Polymères à faible dispersité obtenus par amorçage à la lumière infrarouge proche et au moyen d'un catalyseur au fer Withdrawn EP4267633A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020134606.9A DE102020134606A1 (de) 2020-12-22 2020-12-22 Polymere mit geringer Dispersität durch Initiierung mit nahem Infrarotlicht und einem Eisenkatalysator
PCT/EP2021/086839 WO2022136292A1 (fr) 2020-12-22 2021-12-20 Polymères à faible dispersité obtenus par amorçage à la lumière infrarouge proche et au moyen d'un catalyseur au fer

Publications (1)

Publication Number Publication Date
EP4267633A1 true EP4267633A1 (fr) 2023-11-01

Family

ID=80112236

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21843905.7A Withdrawn EP4267633A1 (fr) 2020-12-22 2021-12-20 Polymères à faible dispersité obtenus par amorçage à la lumière infrarouge proche et au moyen d'un catalyseur au fer

Country Status (4)

Country Link
EP (1) EP4267633A1 (fr)
CN (1) CN116601181A (fr)
DE (1) DE102020134606A1 (fr)
WO (1) WO2022136292A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6140384A (en) 1996-10-02 2000-10-31 Fuji Photo Film Co., Ltd. Photopolymerizable composition containing a sensitizing dye with cyano or substituted carbonyl groups
DE102012205807A1 (de) 2012-04-10 2013-10-10 Few Chemicals Gmbh Cyanin-Farbstoffe
US8927197B2 (en) 2012-11-16 2015-01-06 Eastman Kodak Company Negative-working lithographic printing plate precursors
CN111040060B (zh) * 2019-12-27 2020-12-29 苏州大学 近红外光热转化下的乙烯基类单体的“活性”自由基聚合方法

Also Published As

Publication number Publication date
CN116601181A (zh) 2023-08-15
WO2022136292A1 (fr) 2022-06-30
DE102020134606A1 (de) 2022-06-23

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