Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/35—Non-linear optics
  • G02F1/355—Non-linear optics characterised by the materials used
  • G02F1/361—Organic materials
  • G02F1/3615—Organic materials containing polymers
  • G02F1/3617—Organic materials containing polymers having the non-linear optical group in a side chain
• • 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
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3836—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing azo groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3838—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing cyano groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/384—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing nitro groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/675—Low-molecular-weight compounds
  • C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
  • C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
  • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences

Definitions

• the present invention relates to block copolymers which may exhibit activity in non-linear optics.
• It relates more particularly to block copolymers comprising organosiloxane blocks and polyurethane blocks which can be oriented under the effect of an electric or magnetic field.
• polymers are often used to make thin films.
• polymers are often used to make thin films.
• polymers comprising hyperpolarizable groups attached to the main chain of the polymer via more or less long hydrocarbon chains, and polymers obtained by polymerization of two antagonistic monomers, at least one of which comprises reactive polymerization functions carried by a hyperpolarisable group.
• These polymers are generally used in the form of a film or as a coating for an element of an optical, electro-optical device. These films or coating generally have a regular thickness of between a few microns and a few tens of microns.
• these films must have very good film-accessibility and also good mechanical resistance and to attack by external elements. It is also desirable that these polymers adhere to the substrate on which they are deposited.
• the polymers proposed until now are usually polyurethanes, polyesters or polyamides, that is to say rigid thermoplastic polymers.
• the films obtained are often brittle and have cracks or cracks which affect the functioning of the system.
• certain mechanical properties, such as elasticity or flexibility, are not sufficient to allow the coating to be produced.
• the materials described above, and in particular polymers have a certain structural rigidity.
• these materials When these materials are subjected to an electric field of polarization at a temperature Tg, they acquire a polarization or orientation which generates a quadratic susceptibility. This polarization or orientation tends to decrease and disappear over time, taking into account the residual mobility of the polarizable groups.
• this return to the non-polarized state requires more or less time, depending on the rigidity of the structure of the material.
• the system may only be active when a control field is applied.
• the materials constituting this system must have a high activity in non-linear optics, but only when they are subjected to the control field, these materials having to regain their non-polarized state very quickly as soon as the electric or magnetic field is eliminated.
• the present invention particularly aims to provide an activatable material to make it active in non-linear optics, but becoming inactive very quickly upon removal of the activation source.
• the invention provides an activatable material characterized in that it comprises a block copolymer consisting of an elastomeric block and a thermoplastic block, the thermoplastic block comprising hyperpolarizable groups.
• copolymers have two glass transition temperatures which can be assigned respectively for the temperature below the elastomeric part and for the highest at the thermoplastic part.
• the block copolymers have a glass transition temperature close to or lower than ambient temperature while the other glass transition temperature is higher than ambient temperature.
• ambient temperature is meant a temperature between 15 ° C and 30 ° C.
• the elastomeric blocks of the polymer constitute at least 10% of the molecular weight Mn of the block copolymer.
• the rigid thermoplastic sequences have great mobility with respect to one another, allowing on the one hand rapid and easy polarization of the hyperpolarizable groups and on the other hand rapid depolarization of these.
• the elastomeric sequence consists of a chain of recurrent polysiloxane motifs.
• thermoplastic sequence consists of a series of recurring units of urethane, ester, amide, ether, imide type comprising hyperpolarisable groups incorporated in the chain of the motif or grafted on this chain, as described in patent 2604440, for example.
• the activatable block polymer is an organopolysiloxane and polyurethane block polymer constituted by a chain of recurrent polysiloxane units A or A1 and of polyurethane recurring units B, B1, C or C1. These recurring reasons have the following general formulas:
• recurring reason A recurring pattern A1: recurring reason B: recurring reason B1: recurring pattern C: recurring motif C1: in which :
• - D which may be absent, represents the group -O- or -NH-
• - Z represents a divalent radical carrying a polysiloxane block having the formula: in which :
• R represents an aliphatic or aromatic hydrocarbon radical which may be halogen, and Y, Y ′ hydrocarbon radicals,
• G 2 represents a divalent radical comprising from 2 to 20 carbon atoms of aliphatic, aromatic, arylaliphatic or alkylaromatic hydrocarbon nature corresponding to the rest of the diisocyanate OCN-G 2 -NCO,
• G 3 represent a radical G 1 or a divalent hydrocarbon radical corresponding to the remainder of a diol containing from 2 to 20 carbon atoms, and
• n 1 can be equal to 0.
• n 1 , n 2 are between 10 and 4000.
• the block copolymer comprises at least one block B, B1, C or C1 comprising the radical G 1 .
• polysiloxane sequences by their elastomeric property provide a certain flexibility and elasticity compared to a urethane polymer which would only comprise units B, B 1 , C or C 1 .
• this block polymer which will generally be in the form of a gum, allows an orientation of the hyperpolarizable groups by an activation field from ambient temperature and even above it.
• the radical G 1 has as general formula in which :
• R 8 represents a benzenic radical substituted or not by a lower alkyl radical (from C 1 to C 6 ).
• R9 represents a lower alkylene radical.
• U represents a group comprising a delocalized electron radical and at least one electron accepting group (A).
• the preferred U groups of the invention are:
• a 1 , A 2 , A 3 identical or different represent hydrogen, an alkyl radical, an electron accepting radical (A), ⁇ ! S cannot simultaneously represent hydrogen and an alkyl radical.
• R 4 , R 3 represent a lower alkyl radical or an electron acceptor radical (A).
• R 6 represents hydrogen, a lower alkyl radical or an electron acceptor radical (A).
• the preferred electron acceptor radicals (A) are the cyano or nitro radicals.
• the radicals Y and Y ′ are alkylene, cycloalkylene, arylene, alkylarylene or arylalkylene hydrocarbon radicals, or groups comprising a heteroatom in the chain.
• the radical G 2 represents an alkylene radical comprising from 2 to 12 carbon atoms, cyclohexylene or cyclopentylene, phenylene, methylphenylene or dimethylphenylene radicals, or also a group of two groups chosen from alkylene groups having from 2 to 12 carbon atoms, the cyclohexylene, cyclopentylene, phenylene, methylphenylene or dimethylphenylene radicals linked together by a valence bond, an oxygen atom, an alkylene or alkylidene group having from 1 to 4 carbon atoms.
• diisocyanates suitable for the invention:
• diisocyanates can be used separately or in the form of mixtures of several of them.
• the hydrocarbon residues of the HO-G-OH diols; HO-G 3 -OH when they do not represent the group G 1 are alkylene radicals comprising from 2 to 12 carbon atoms, deè cyclohexylene or cyclopentylene radicals, a group of two groups chosen from alkylene groups having from 2 to 12 atoms of carbon or the cyclohexylene or cyclopentylene radicals, linked together by a valential bond, an oxygen atom, an alkylene or alkylidene group having from 1 to 4 carbon atoms.
• diols suitable for the invention propanediol, ethanediol, hexanediol, pentanediol, pentenediol, butenediol.
• a subject of the invention is also a process for obtaining the organopolysiloxane and polyurethane block copolymer described above and consisting in reacting a difunctional compound of formula XZX 'with at least one diol of formula HO-G-OH, HO-G 1 - OH, HO-G 3 -OH and with at least one diisocyanate of formula OCN-G 2 -NCO, the identical symbols X and X ′ represent a hydroxyl group, an isocyanate group, an acid group or an amino group, the other symbols G, G 1 , G 2 , G 3 have the meanings indicated above.
• the various difunctional compounds are introduced in an amount such that the ratio of all of the isocyanate groups relative to the other antagonistic groups is between 0.9 and 1.1, preferably between 0.95 and 1.05.
• the content of polysiloxane group in the reaction mixture is determined, as well as the molecular weight of the difunctional compound X-Z-X '.
• the content of HO-G 1 -OH diol in the reaction medium is determined as a function of the properties in nonlinear optics desired.
• the mass ratio of diols not active in ONL compared to active diols in ONL can be between 0 and 1.
• This polymerization can be carried out in bulk or in a solvent medium.
• suitable solvents halogenated hydrocarbons, tetrahydrofuran, tetramethylurea, dimethylethylurea (DMEU), dimethylacetamide (DMAC), dimethyformamide (DMF), N-methylpyrrolidone (NMP), or analogues.
• copolymer of the invention can be used alone or in admixture with other active or non-active polymers in non-linear optics.
• This copolymer is generally shaped, for example by extrusion, molding, filming or spinning.
• the copolymer is used in the form of a film, for example to form a coating, obtained by the technique called "spin-coating".
• This film-forming can be carried out by any means such as for example by melting, softening or by dissolving in a solvent and evaporation of the latter.
• the block copolymer thus obtained can be used in devices of the electrooptical modulator type in guided or non-guided configuration, directional and bistable electrooptic coupler.
• the activity in nonlinear optics of these materials is determined by measuring the cubic or quadratic susceptiblities.
• the activity of materials in nonlinear optics is determined by the measurement of second, third or umpteenth order susceptibilities.
• ⁇ 1 , ⁇ 2 , ⁇ 3 represent the linear and non-linear susceptibilities of the material.
• the coefficient ⁇ 1 reflects its activity in linear optics.
• the coefficients ⁇ 2 and ⁇ 3 represent the second and third order susceptibilities respectively.
• the odd-order susceptibilities such as the susceptibility ne 3 are never zero for all materials.
• even order susceptibilities such as the quadratic susceptibility ⁇ 2 are zero for centrosymmetric materials.
• KDP potassium dihydrogen phosphate
• the measurement of the susceptibility ⁇ 2 is generally carried out at frequencies (-2 ⁇ ; ⁇ , ⁇ ) in a doubling harmonic experiment described in the article by SKKURTZ published in Quantum Electronics ed. H.RABIN, CLTANG académie Press, 1975, tome I pages 209 - 281.
• ⁇ 2 at frequencies (- ⁇ ; ⁇ , o) in an electrooptical experiment.
• the film is deposited on a glass slide covered with a transparent conductive oxide (SnO 2 ).
• the outer face of the film is covered by a semi-transparent gold layer, the oxide and the gold serving as electrodes by which the film is polarized to make it non-centrosymmetric.
• the assembly is placed on an optical bench of polarimetry similar to that described in the article "Characterization of polymeric non linear optical materials", G. KHANARIAN, T. CHE, RN De Martino et al. Proceedings of SPIE - Int. Soc. Opt. Eng. Vol 824, p. 72.
• the film is subjected to an alternating voltage ⁇ v of 1 KHZ, 10 volts.
• This voltage ⁇ v modulates the phase shift ⁇ between the waves s and p by a quantity ⁇ ⁇ which is detected by synchronous detection.
• n is the index of the film, i the angle of incidence of the beam by the film, and ⁇ the wavelength.
• the mass obtained is poured into a liter of water, then filtered and washed.
• n 7 and m is 4.
• Example 2 As in Example 1, the hyperpolarizable diol of Example 1 (2.9 g) reacts with a polysiloxane monomer (12 g) of the following formula:
• n equal to 5 or 6.
• This polysiloxane monomer contains 0.14 isocyanate equivalent per 100 grams. This reaction is carried out in dry DMEU medium and in the presence of dibutyl tin dilaurate.
• Example 1 is repeated, but using as hyperpolarizable diol, the compound of the following formula:
• Example 3 is repeated, with the hyperpolarizable diol the following compound:
• This prepolymer contains 0.217 mole of NCO equivalent per 100 g of prepolymer.
• the product collected is a gum having a glass transition temperature equal to about 18 ° C.
• the polymer structure confirmed by spectral analysis, includes:
• the determination of its electrooptical activity at a wavelength of 633 nm is carried out by polarimetry according to the method described above.
• the time for the susceptibility ⁇ 2 333 to return to 0 has been determined.

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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)
• Physics & Mathematics (AREA)
• Nonlinear Science (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Polyurethanes Or Polyureas (AREA)

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Citations (8)

• 1989
  • 1989-07-28 FR FR8910197A patent/FR2650287B1/fr not_active Expired
• 1990
  • 1990-07-26 EP EP19900912269 patent/EP0436708A1/fr not_active Withdrawn
  • 1990-07-26 JP JP51147390A patent/JPH04506874A/ja active Pending
  • 1990-07-26 WO PCT/FR1990/000567 patent/WO1991002018A1/fr not_active Application Discontinuation

Patent Citations (8)

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