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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
  • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
  • B01J19/121—Coherent waves, e.g. laser beams
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
  • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
  • B01J19/122—Incoherent waves
  • B01J19/128—Infrared light
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures

Definitions

• the invention relates to a method for the polymerization of monomer and / or oligomer units according to the preamble of claim 1 and the use of infrared light pulses according to the preamble of claim 14.
• WO 2006/069448 A2 a method for the removal of material by means of infrared light laser pulses known, in which the energy of the infrared light is converted into heat energy of the material to be removed.
• superheated points are generated within the material to be removed, in which the temperature is above the evaporation point of at least one component of the material to be removed.
• the present invention has for its object to provide a method in which a polymerization of monomer and / or oligomer units to polymer units is accomplished substantially without increasing the temperature of the material to be polymerized. Furthermore, the invention has for its object to provide a new use for infrared light pulses.
• the invention is based on the fundamental idea, not to introduce heat by means of infrared light pulses in a system to be reacted, but specifically to stimulate bonds within the molecules to be reacted so as to break up these bonds and the To allow recombination of atoms previously involved in the bonds.
• radicals can also be generated in this way.
• crosslinking reactions can be initiated, selectively controlled and spatially arranged.
• the polymerizations to be carried out according to the invention can also be, for example, polycondensation or polyaddition reactions.
• the energy required for the polymerization is provided by infrared light pulses in a process for the polymerization of monomer and / or oligomer units to polymer units.
• the infrared light pulses have a wavelength of 2500 to 20,000 nm, an intensity of more than 10 14 W / m 2 , a duration of more than 8 femtoseconds (fs) and less than 3 picoseconds (ps) and a substantially (ie predominantly ) linear polarization.
• infra-red light pulses of duration less than 3 ps, more preferably less than 1 ps, and most preferably less than 500 fs, intra- and intermolecular energy redistributions which could lead to thermal heating of the molecule are avoided.
• pulse durations of more than 8 fs, in particular more than 10 fs, in particular more than 50 fs and very particularly more than 100 fs are necessary.
• the intensity of the infrared light pulses is necessary for the intensity of the infrared light pulses to be greater than 10 4 W / m 2 , in particular greater than 10 15 W / m 2 , in particular greater than 10 16 W / m 2 and especially greater than 10 17 W / m 2 . Since such high intensities can currently only be generated with lasers, an infrared light laser is expediently used as the infrared light source.
• the infrared light pulses also have a predominantly linear polarization whose direction can be changed. Since the infrared light absorption is given by the vector direction of the vibration transition dipole moments (tdm), mainly monomer and oligomer units will absorb infrared light whose vibration transition dipole moment is aligned parallel to the infrared laser light polarization direction. Thereby, the direction along which the polymerization takes place can be set and changed with the infrared laser light polarization. As a result, polymers with significantly different properties along different spatial directions can be produced, which is not possible by heating, since this is a largely isotropic process.
• tdm vibration transition dipole moments
• the infrared light pulses preferably additionally have a negative chirp.
• chirp is meant the property of a light pulse that its frequency changes over the duration of the light pulse
• the energy needed to transfer a vibration from a high vibration level to an even higher vibration level is less than the energy required to transfer a vibration from the ground state to the first higher vibration level, and a negative chirp infrared pulse contributes to that fact to the effect that the frequency decreases with time, so that the energy provided by the infrared light pulse also decreases with time, that is, the infrared light fundamental pulse has first high-energy and later low-energy Consequently, the infrared light pulse is well adapted to the vibration levels to be excited so that an optimal energy transfer can take place.
• Chirped infrared light pulses may be generated, for example, with a deformable mirror or with the passive infrared light pulse shaper described in international patent application WO 2009/135870 A1.
• linearly negatively chirped infrared light pulses are used. This means that the frequency of these infrared light pulses decreases linearly over the entire pulse duration; this is particularly close to the model of the anharmonic oscillator and allows a particularly advantageous energy input into the molecules to be reacted.
• the wavelength of the infrared light pulses is set at 2500 to 20000 nm (4000 cm “1 to 500 cm “ 1 ) such that numerous vibrations of the bonds to be opened and remapped for a polymerization reaction can be excited.
• Preferred wavelength ranges extend from about 3000 nm to about 15000 nm, from about 4000 nm to about 10000 nm or from about 5000 nm to about 8000 nm.
• the infrared light pulses additionally have a polarization. This makes it possible to excite certain bonds whose vibration vectors are aligned along the polarization direction of the infrared light.
• each infrared light pulse in one variant passes over a spectral range of about 2 to about 1000 cm.sup.- 1 .
• a spectral range of about 2 to about 1000 cm.sup.- 1 .
• vibrations which have an absorption spectrum in the absorption spectrum
• suitable spectral ranges which each infrared light pulse sweeps over its lifetime are the ranges of approximately 100 to 900 cm -1 , especially approximately 200 to 800 cm -1 , especially approximately 300 to 700 cm -1 and especially from about 400 to 600 cm "1 .
• the repetition rate of the infrared light pulses is between 0.5 kHz and 200 MHz. In this way, relatively bulky polymer bodies can be produced even in manageable times. Further suitable lower limits for the repetition rate are about 1 kHz, about 10 kHz, about 100 kHz and about 1 MHz. Further suitable upper limits for the repetition rate are approximately 10 MHz, 50 MHz, 80 MHz, 100 MHz, 150 MHz and 170 MHz.
• a plurality of superimposed infrared light pulses are used which differ from one another in at least one parameter.
• This parameter can be, for example, the spectral range and / or the polarization of the infrared light pulses.
• the generation of the plurality of superimposed infrared light pulses can be done in a variant, for example by at least one optical parametric amplifier.
• Such optical parametric amplifiers are suitable for influencing both the wavelength and the polarization of an infrared light pulse.
• any optical parametric amplifier generally known to the person skilled in the art can be used.
• Common optical parametric amplifier crystals from which the optical parametric amplifiers can be made are, for example, lithium niobate and lithium tantalate, betabarium borate (BBO), silver thiogolate (AgGaS 2 ), potassium deuterium phosphate (KDP) and potassium titanyl arsenate (KTA ).
• the penetration depth into the monomer and / or oligomer units to be polymerized is basically arbitrary, but depends on the properties of the monomer and / or oligomer units and of the polymer units formed. If the polymer units absorb the infrared light of the wavelength used well, it is not possible to penetrate into deeper layers of monomer and / or oligomer units, if polymer units have already been formed in a higher layer. However, when working with polymer units that do not absorb the infrared light of the wavelength used, it is also possible to penetrate after the polymerization of higher layers still deeper layers of monomer and / or oligomer units and initiate polymerization reactions there.
• the method is carried out using suitable focusing lenses to additionally focus the infrared light beam.
• suitable focusing lenses to additionally focus the infrared light beam.
• the process is carried out in such a way that the polymerization takes place in a localized space which is transversely smaller than 10 ⁇ m, in particular smaller than 5 ⁇ , in particular less than 2 ⁇ and especially smaller than 1 ⁇ and longitudinally less than 20 ⁇ , in particular less than 10 ⁇ , in particular less than 50 ⁇ , in particular less than 2 ⁇ and in particular less than 1, 5 ⁇ .
• transversal and “longitudinal” refer to the propagation direction of the infrared light pulses.
• the process can be carried out with substances in any state of aggregation, the process is carried out in a variant of the process in a liquid system. That is, the monomer and / or polymer units to be reacted are either present as liquid substances and / or are dissolved in a liquid solvent.
• solvents for example, alcohols such as methanol, ethanol, propanol, butanol and corresponding diols such as 1, 2-ethanediol and 1, 4-butanediol or non-alcoholic, organic solvents such as carbon tetrachloride or aqueous solvents can be used.
• the solvent is selected both in terms of its chemical nature and in terms of its amount used in that it can slow down exothermic or exergonic polymerization reactions or prevent their spontaneous operation entirely. This can be achieved, for example, by using the same amount of solvent or even ten times as much solvent as the monomer and / or oligomer units to be reacted.
• the monomer and / or oligomer units to be polymerized are basic units of a plastic.
• the plastic may optionally have microstructured region.
• Suitable preparable plastics are, for example, polyurethane (PU), polyethylene terephthalate (PET), polyvinyl chloride (PVC) or polypropylene (PP).
• the corresponding basic units to be polymerized can therefore be, for example, isocyanates, terephthalic acid, ethylene glycol, vinyl chloride and propene.
• a variant of the method it is carried out such that certain areas of the polymer produced have a higher degree of polymerization than other areas of the polymer.
• This can on the one hand - as just mentioned - be achieved by the targeted steering of the infrared light pulses to certain areas of a solution or composition of the substances to be polymerized. For example, certain areas can be irradiated for a longer time with infrared light pulses, so that sets a higher degree of polymerization here.
• this variant of the method can also be accomplished by - as explained above - polarized infrared light pulses are used to specifically specific binding or binding directions to stimulate the reaction, but to save others from a reaction.
• the two aforementioned variants are combined with one another, so that a plastic is produced which has at least one elastic and at least one plastic region.
• the elastic region is a region with a lower degree of polymerization, while the plastic region is a region within the plastic having a higher degree of polymerization.
• cross-links by deliberately introducing cross-links, a higher plasticity of certain areas can be achieved, while other plastic areas maintain their elastic properties. This makes it possible to produce microstructured plastics which have individually adapted properties and consequently can be adapted to the specific requirements of a wide variety of possible uses.
• microstructuring it is possible, for example, to introduce labels in a plastic or in another polymer or in objects that consist of this plastic or other polymer, without additionally having to apply a label on the plastic or the polymer.
• the durability of such logos can be significantly increased and extend their life as significantly.
• the polymer has anisotropic properties that are increased or decreased by 50% in a first direction of the polymer in terms of properties in a second direction.
• the second direction differs from the first direction in particular by at least or around 10 °, 30 °, 45 °, 60 °, 75 ° or 90 °.
• the object is also achieved by the use of infrared light pulses having the features of claim 14. Accordingly, the infrared light pulses have a wavelength of 2500 to 20,000 nm, an intensity of more than 10 15 W / m 2 , a duration of more than 8 fs and less than 3 ps and a substantially linear polarization and are used for the polymerization of monomer and / or oligomer units used.
• infrared light pulses for polymerization is suitable for producing a microstructured polymer. Also in this regard, reference is made to the above statements. Further characteristics and details of the present invention will be explained in more detail with reference to the figures and an example. Show it:
• Fig. 1 shows the structural formula of toluene-2,4-diisocyanate and Fig. 2 shows an example of a structured polymer.
• FIGS. 1 and 2 will be explained in more detail in connection with the following example.
• TDI as the monomer unit to be polymerized are mixed with 1 ml of anhydrous 1, 4-butanediol as solvent and reactant, so that there is a ratio of 10 to 1 (based on the volume of each substance used) between solvent and monomer units to be polymerized.
• 1, 4-butanediol as solvent and reactant
• the output frequency of the laser is 2280 cm " 1 .
• Each laser pulse has a duration of 500 fs and covers a spectral range of 100 cm -1 (that is, it has a half width of 100 cm -1 ).
• the laser pulses used are negatively linear chirped so that their frequency continuously decreases from an initial 2280 cm -1 to 2180 cm -1 during the pulse duration of 500 fs.
• the light emitted by the infrared laser is also linearly polarized.
• the repetition rate of the laser is 100 kHz, the focus is 20 ⁇ .
• TDI The structural formula of TDI is shown in FIG.
• the arrows next to the isocyanate groups of the TDI indicate the vibrational transition dipole moment vectors of the two isocyanate groups. Since these Schwingungsübergangsdipolmomentvektoren are offset by 90 ° to each other, targeted by the use of polarized light only one of the two isocyanate groups per molecule can be excited to the reaction.
• a possible reaction scheme is as follows: By excitation of the isocyanate groups with the infrared light pulses, the double bonds between the nitrogen atom or the carbon atom and between the carbon atom and the oxygen atom are broken. The reaction with a hydroxy group of 1, 4-butanediol then leads to a protonation of the nitrogen atom and to form an additional carbon-oxygen compound and to a reformation of the double bond between the carbon atom and the oxygen atom. The result is a urethane group (-NH-CO-0-). Due to the difunctionality of the TDI and the 1, 4-butanediol so linear polyurethanes can be formed.

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• Chemical Kinetics & Catalysis (AREA)
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• Investigating Or Analysing Materials By Optical Means (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2011
  • 2011-06-07 DE DE102011050894A patent/DE102011050894A1/de not_active Withdrawn
• 2012
  • 2012-06-06 WO PCT/EP2012/060705 patent/WO2012168302A1/de active Application Filing
  • 2012-06-06 US US14/124,480 patent/US9617368B2/en active Active
  • 2012-06-06 EP EP12730410.3A patent/EP2718005B1/de not_active Not-in-force

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