WO2022136292A1 - 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 Download PDF

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Publication number
WO2022136292A1
WO2022136292A1 PCT/EP2021/086839 EP2021086839W WO2022136292A1 WO 2022136292 A1 WO2022136292 A1 WO 2022136292A1 EP 2021086839 W EP2021086839 W EP 2021086839W WO 2022136292 A1 WO2022136292 A1 WO 2022136292A1
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providing
polymers
iron
range
atrp
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PCT/EP2021/086839
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German (de)
English (en)
Inventor
Bernd Strehmel
Veronika Strehmel
Ceren Kütahya
Nicolai Meckbach
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Phosuma Photonic & Sustainable Materials Gmbh
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Priority to CN202180085618.0A priority Critical patent/CN116601181A/zh
Priority to EP21843905.7A priority patent/EP4267633A1/fr
Publication of WO2022136292A1 publication Critical patent/WO2022136292A1/fr

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    • 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.
  • ATRP Atom transfer based radical polymerization
  • RP radical polymerizations
  • controlled or "living" radical polymerizations allows the synthesis of tailored polymeric materials with predefined molecular weights and narrow molecular weight distributions.
  • ATRP is controlled by a reversible activation/deactivation equilibrium with a transition metal catalyst and an alkyl halide. In ATRP equilibrium, the lower oxidation state transition metal complex activates the alkyl halide to generate an initiating radical to initiate radical polymerization and the higher oxidation state transition metal complex.
  • 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.
  • the inhomogeneous distribution of the molar masses of the polymer chains during polymer production is referred to as the dispersity and is calculated using the ratio of the average weight average to the average number average of the polymers.
  • the distribution can be well described using a Poisson distribution.
  • Desirable are polymers with the lowest possible dispersity, ie, low molar mass distribution, which have values in the range from 1.3 to 1.2 and, if possible, even below that.
  • KÜTAHYA ET AL report with the title "NIR Light-Induced ATRP for Synthesis of Block Copolymers comprising UV-absorbing Moieties" in: Chemistry - A European Journal, 26, 10444-10451 (2020) on the use of monomers with UV absorbing units that have a UV filter effect using heptamethines and a Cu(II) catalyst. Polymerization under oxygen was not possible. Furthermore, it is known that the use of copper connections is problematic for numerous applications.
  • MMA is polymerized in MeCN in the presence of ethyl bromophenyl acetate (EBPA) as an ATRP starter and FeCh.
  • EBPA ethyl bromophenyl acetate
  • WO 2014 078140 A1 relates to a method for providing a lithographic printing plate, the imageable layer containing a compound for providing free radicals on infrared radiation in the presence of the infrared radiation absorber, a free-radically polymerizable compound and an infrared radiation absorber from the cyanine group includes, which assume the function of a sensitizer. There is no controlled synthesis of polymers based on a living radical polymerization mechanism.
  • DE 10 2012 205807 A1 discloses cyanines comprising sulfoaryl and N-sulfoalkyl groups or trialkylammoniumalkyl groups, the alkyl group having 1-4 carbon atoms, and a methine chain having a five- or six-membered ring structure is bridged; and a differentially substituted pyrimidine trione at its meso position and a reactive group enabling attachment to supports, wherein at least one oxygen atom, preferably one oxygen atom, para to attachment to the methine chain, in which pyrimidine trione is optional or is replaced by a sulfur atom.
  • pyrimidine trione is optional or is replaced by a sulfur atom.
  • 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.
  • the invention relates to polymers with a dispersity of less than 1.4, preferably from 1.0 to 1.35 and in particular about 1.1, which are obtainable or are obtained by the following steps:
  • 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.
  • the resulting polymers are 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 gives the polymers in the required purity, with the NMR spectra generally no longer showing any recognizable amounts of residual solvent and monomer.
  • Another object of the invention relates to the use of the polymers according to the invention or the products according to the process according to the invention for the production of block copolymers and polymeric networks with a uniform network arc spacing. These are suitable for commercial applications requiring high mechanical stability, which is provided by improved mesh arc spacing uniformity.
  • this method of the polymers according to the invention or their products can be used for the production of paint additives.
  • the reaction was carried out in a photoreactor as shown in Figure 1, which was in the form of a Schlenk tube (diameter 18 mm) equipped with a magnetic stirring bar and a Teflon screw cap.
  • 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 sample was then exposed to NIR radiation using four NIR LEDs (790 nm) arranged around the photoreactor with an angle of 90° between each LED and a spacing of 11.0 mm.
  • the light intensity of each LED was 100 mW ⁇ cm 2 within the exposed area at the middle height on the surface of the tube.
  • the Schlenk tube was sealed in a light-tight box, the sample was cooled with an air flow around the reactor and stirred with a magnetic stirrer during the irradiation.
  • 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 1/5 Structure of the irradiation apparatus from the top view
  • 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;

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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)
  • 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.
PCT/EP2021/086839 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 WO2022136292A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202180085618.0A CN116601181A (zh) 2020-12-22 2021-12-20 通过近红外光和铁催化剂引发的具有低分散性的聚合物
EP21843905.7A 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

Applications Claiming Priority (2)

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DE102020134606.9A DE102020134606A1 (de) 2020-12-22 2020-12-22 Polymere mit geringer Dispersität durch Initiierung mit nahem Infrarotlicht und einem Eisenkatalysator
DE102020134606.9 2020-12-22

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Citations (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
WO2014078140A1 (fr) 2012-11-16 2014-05-22 Eastman Kodak Company Précurseur de plaque d'impression lithographique négative
CN111040060A (zh) * 2019-12-27 2020-04-21 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

Patent Citations (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
WO2014078140A1 (fr) 2012-11-16 2014-05-22 Eastman Kodak Company Précurseur de plaque d'impression lithographique négative
CN111040060A (zh) * 2019-12-27 2020-04-21 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

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
"Photophysics and photochemistry of NIR absorbers derived from cyanines: key to new technologies based on chemistry 4.0", BEILSTEIN J ORG CHEM, vol. 16, 2020, pages 415 - 444
C. KÜTAHYA: "Nahinfrarot-sensibilisierte photoinduzierte ATRP mit einer Kupfer(II)-Katalysatorkonzentration im ppm-Bereich", ANGEWANDTE CHEMIE, vol. 130, 2018, pages 8025 - 8030
CEREN KÜTAHYA ET AL: "Nahinfrarot-sensibilisierte photoinduzierte ATRP mit einer Kupfer(II)-Katalysatorkonzentration im ppm-Bereich", ANGEWANDTE CHEMIE, WILEY - V C H VERLAG GMBH & CO. KGAA, DE, vol. 130, no. 26, 16 May 2018 (2018-05-16), pages 8025 - 8030, XP071375302, ISSN: 0044-8249, DOI: 10.1002/ANGE.201802964 *
KÜTAHYA ET AL.: "NIR Light-Induced ATRP for Synthesis of Block Copolymers comprising UV-absorbing Moieties", CHEMISTRY - A EUROPEAN JOURNAL, vol. 26, 2020, pages 10444 - 10451
PAN ET AL., MACROMOLECULES, vol. 48, 2015, pages 6948 - 6954
PAN XIANGCHENG ET AL: "Photomediated controlled radical polymerization", PROGRESS IN POLYMER SCIENCE, vol. 62, 14 July 2016 (2016-07-14), pages 73 - 125, XP029835516, ISSN: 0079-6700, DOI: 10.1016/J.PROGPOLYMSCI.2016.06.005 *
S. DADASHI-SILAB, CHE-MICAL REVIEWS, vol. 116, 2016, pages 10212 - 10275
STREHMEL BERND ET AL: "Photophysics and photochemistry of NIR absorbers derived from cyanines: key to new technologies based on chemistry 4.0", BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, vol. 16, 1 January 2020 (2020-01-01), pages 415 - 444, XP055870753, Retrieved from the Internet <URL:https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-16-40.pdf> DOI: 10.3762/bjoc.16.40 *
VON C. SCHMITZ: "Neue Hochleistungs-LEDs ermöglichen Photochemie für die Nahinfrarot-sensibilisierte radikalische und kationische Photopolymerisation", ANGEWANDTE CHEMIE, vol. 131, no. 13, 2019, pages 4445 - 4450
X. PARI ET AL., MACROMOL. RAPID COMMUN, vol. 38, 2017, pages 1600651
X.PAN ET AL., MACROMOL. RAPID COMMUN., vol. 38, 2017, pages 1600651
XUE ET AL., ANGEW. CHEMIE, vol. 47, 2008, pages 6426 - 6429

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EP4267633A1 (fr) 2023-11-01
DE102020134606A1 (de) 2022-06-23
CN116601181A (zh) 2023-08-15

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