FR2650287A1 - - Google Patents

Abstract

The present invention relates to sequenced polymers comprising hyperpolarisable groups. These sequenced polymers comprise elastomeric (organopolysiloxane) and thermoplastic (polyurethane) sequences. The hyperpolymerisable groups are present especially in the thermoplastic sequences. These polymers may be polarised under the effect of a polarisation field in the low-temperature ranges like ambient temperature and very quickly revert to their unpolarised state once the polymerisation field is removed.

Description

ADJUSTABLE SEQUENCE COPOLYHERES
TO BE ACTIVE IN NON-LINEAR OPTIOUE
The present invention relates to block copolymers which may exhibit activity in non-linear optics.

 It relates more particularly to block copolymers co taking organosiloxane blocks and polyurethane blocks orientable under the effect of an electric or magnetic field.

 J.ZTSS and I LEWUX in the article published in "L'écho des Recherches", 1st quarter 1987 under the title "Organic molecules and optical signal processing" indicate that the development of optical telecommunications requires the production of components using materials high second or third order nonlinear susceptibility.

 Numerous compounds, both inorganic and organic, are used in different forms such as solutions, polymers, doped polymers, monomolecular layers, liquid crystals, single crystals, liquid crystal polymers or the like.

 Among these compounds, polymers are often used to make thin films. Among the systems using polymers, we find two classes.

 A first class formed by systems comprising a polymer which is not active in non-linear optics in which an active compound in non-linear optics is dissolved or dispersed. This system is generally called the "Guest-host" system.

 A second class formed by functionalized polymers in which hyperpolarisable groups are grafted by covalent bonds on the backbone of the polymer.

 Among these functionalized polymers, a distinction can be made between polymers comprising hyperpolarisable groups attached to the main chain of the polymer by means of more or less long hydrocarbon chains, and polymers obtained by polymerization of two opposing oneros, at least one of which comprises reactive polymerization functions carried by a hyperpolarizable group.

 By way of example of functionalized polymers with pendant hyperpolarisable groups, mention may be made of European patents Nos. 271 730, 263 02i, 214 828.

 As an example of polymers with hyperpolarisable groups incorporated in the main chain, mention may be made of Japanese patent applications Nos. 63 175838, 63 175837, 63 175836, 63 175834.

 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.

 For this, 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 so far 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. In addition, 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. When these materials are subjected to an electric polarization field 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. However, this return to the non-polarized state requires more or less time, depending on the rigidity of the structure of the material.

 These materials are used for signal processing for example.

 In certain applications such as for example electro-optical modulators in guided or non-guided configuration, directional couplers, the system may only be active when a control field is applied. Thus, 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 object of the present invention is in particular to provide an activatable material to make it active in non-linear optics, but becoming inactive very quickly as soon as the activation source is removed.

 To this end, the invention provides an activatable material characterized in that it comprises a block copolymer consisting of an elastomeric block and a therooplastic block, the thermoplastic block comprising hyperpolarizable groups.

 These 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.

 According to the invention, the block copolymers have a glass transition temperature close to or lower than room temperature while the other glass transition temperature is higher than room temperature.

 By ambient temperature is meant a temperature between 150C and 300C.

 According to another characteristic of the invention, the elastomeric blocks of the polymer constitute at least 10% of the molecular weight Mn of the block copolymer.

 Thus, the rigid thermoplastic sequences have great mobility with respect to each other, allowing on the one hand rapid and easy polarization of the hyperpolarizable groups and on the other hand rapid depolarization of these.

 According to another characteristic of the invention, the elastomeric sequence consists of a series of recurrent polysiloxane motifs.

 According to another characteristic of the invention, the thermoplastic sequence consists of a series of recurring units of urethane, ester, amide, ether, imide type comprising hyperpolarizable groups incorporated in the chain of the motif or grafted on this chain, as described in patent 2604440, for example.

 In a preferred embodiment of the invention, the activatable sequenced polymer is an organopolysiloxane and polyurethane block polymer constituted by a chain of recurrent polysiloxane A or Ai units and of polyurethane recurring units B, B1, C or Cl.

motif récurrent Ai

motif récurrent B

motif récurrent Bi

motif récurrent C

motif récurrent Ci

dans lesquelles
- D : qui peut être absent, représente le groupement -O- ou -NH
- Z représente un radical divalent porteur d'un bloc polysilo
xanique ayant pour formule

dans laquelle
- R représente un radical hydrocarboné aliphatique ou aromatique
pouvant être halogéné, et Y,Y' des radicaux hydrocarbonés,
- G2 représente un radical divalent comprenant de 2 à 20 atomes de
carbone de nature hydrocarbonée aliphatique, aromatique, arylali
phatique ou alkylaromatique correspondant au reste du diisocyanate
oCN-G2-NCO,
- G1 un radical hyperpolarisable présentant une distribution
électronique délocalisée, et correspondant au reste du diol
HO-G1-OH,
- G, G3 représentent un radical G1 ou un radical hydrocarboné
divalent correspondant au reste d'un diol comportant de 2 à 20 ato
mes de carbones, et
- nlr n2 identiques ou différents sont un nombre compris entre 1 et
4000, ni pouvant être égal à 0.These recurring patterns have the following general formulas recurring pattern A

recurring pattern Ai

recurring pattern B

recurring pattern Bi

recurring pattern C

recurring pattern Ci

in which
- D: which may be absent, represents the group -O- or -NH
- Z represents a divalent radical carrying a polysilo block
xanic having the formula

in which
- R represents an aliphatic or aromatic hydrocarbon radical
can be halogenated, and Y, Y ′ hydrocarbon radicals,
- G2 represents a divalent radical comprising from 2 to 20 atoms of
aliphatic, aromatic, arylali hydrocarbon carbon
phatic or alkylaromatic corresponding to the rest of the diisocyanate
oCN-G2-NCO,
- G1 a hyperpolarizable radical having a distribution
delocalized electronics, and corresponding to the rest of the diol
HO-G1-OH,
- G, G3 represent a G1 radical or a hydrocarbon radical
divalent corresponding to the rest of a diol containing from 2 to 20 ato
carbon, and
- nlr n2 identical or different are a number between 1 and
4000, nor can be equal to 0.

 Preferably nj, n2 are between 10 and 4000.

In addition, the block copolymer comprises at least one block B,
B1, C or Ci containing the radical G1.

 Thus, the polysiloxane sequences by their elastomeric property provide a certain flexibility and elasticity compared to a urethane polymer which would only comprise units B, Bi, C or C1.

 The flexibility of this block polymer, which will generally be drilled with an eraser, allows orientation of the hyperpolarizable groups by a field of activation from room temperature and even above it.

 Furthermore, this flexibility also allows rapid depolarization of these groups as soon as the activation field is removed.

dans laquelle
R8 représente un radical benzénique substitué ou non par un radical alkyl inférieur (de Ci à C6).According to another characteristic of the invention, the radical G1 has the general formula

in which
R8 represents a benzene radical substituted or not by a lower alkyl radical (from C1 to C6).

 R9 represents a lower alkylene radical.

 U represents a group comprising a delocalized electron radical and at least one electron accepting group (A).

dans lesquelles
A1, A2, A3 identiques ou différents représentent l'hydrogène, un radical alkyle, un radical (A) accepteur d'électrons, ils ne peuvent représenter simultanément l'hydrogène et un radical alkyle.The preferred U groups of the invention are

in which
A1, A2, A3 identical or different represent hydrogen, an alkyl radical, an electron accepting radical (A), they cannot simultaneously represent hydrogen and an alkyl radical.

 R4, R5 represent a lower alkyl radical or an electron acceptor radical (A).

 R6 represents hydrogen, a lower alkyl radical or an electron acceptor radical (A).

 The preferred electron acceptor radicals (A) are the cyano or nitro radicals.

According to another characteristic of the invention, the radicals Y and
Y 'are alkylene, cycloalkylene, arylene, alkylarylene or arylakylene hydrocarbon radicals, or groups comprising a heteroatom in the chain.

 According to another characteristic of the invention, the radical G2 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.

By way of example, there may be mentioned as diisocyanates suitable for the invention
- 1,3-diisocyanato propane,
- 1,4-diisocyanato butane,
diisocyanato-1,5 pentane,
- 1,6-diisocyanato hexane,
- 1,4-diisocyanato-2-ethyl butane,
- 1,5-diisocyanato-2-methyl pentane,
- 1,6-dimethyl-2,2,4-hexane diisocyanato,
- 1,6-dimethyl-2,4,4,4-hexane diisocyanato,
- 1,2-diisocyanato cyclohexane,
1,4-diisocyanato cyclohexane,
- bis (isocyanatozethyl) -1,2 cyclobutane,
- bis (4-isocyanato cyclohexyl) methane,
- trimethyl-3,3,5 isocyanatomethyl-5 isocyanato-l cyclohexane,
- bis (isocyanatomethyl) -i, 4 benzene
- bis (isocy # natomethyl) -1,2 benzene
- diphenyl propane diisocyanato,
- diphenyl propane diisocyanato,
- diisocyanato diphenyl ether,
- naphthalene diisocyanato.

 These diisocyanates can be used separately or in the form of mixtures of several of them.

 According to another characteristic of the invention, the hydrocarbon residues of the HO-G-OH diols; HO-G3-OH when they do not represent the group G1 are alkylene radicals comprising from 2 to 12 carbon atoms, cyclohexylene or cyclopentylene radicals, a set of two groups chosen from alkylene groups having from 2 to 12 carbon atoms 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.

 By way of example, there may be mentioned as suitable diols for the invention propanediol; ethanediol, hexanediol, pentanediol, pentènediol, butènediol.

The invention also relates to 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-G1 -OH, HO-G3-OH and with at least one diisocyanate of formula OCN-G2-NCO, the identical symbols X and X' represent a group hydroxyl, an isocyanate group, an acid group or an amine group, the other symbols G,
G1, G2, G3 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.

 Depending on the mechanical properties sought, the content of polysiloxane group in the reaction mixture is determined, as well as the molecular weight of the difunctional compound X-Z-x '.

 Likewise, the content of HO-G1 -OH diol in the reaction medium is determined as a function of the properties in nonlinear optics desired.

Thus, when diols of formula HO-G1 -OH with hyperpolarizable group are used in admixture with diols of formula HO-G-OH or HO-G3-OH not comprising a hyperpolarizable group, the mass ratio of the non-active diols in ONL compared to the active diols in ONL can be between 0 and 1.

 This polymerization can be carried out in bulk or in a solvent medium. By way of example, there may be mentioned as suitable solvents, halogenated hydrocarbons, tetrahydrofuran, tetramethylurea, dimethylethylurea (GOD), dimethylacetamide (DHAC), dimethyforma aid (DWF), ethylpyrrolidone (rice), or the like .

 The 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 ais in shape for example by extrusion, molding, filming or spinning.

 Generally, the copolymer is used in the form of a film, for example to form a coating, obtained by the technique called "Hspin-coating".

 This Dise in the form of film can be carried out by any means such as for example by fusion, softening or by dissolving in a solvent and evaporation of this one.

 The block copolymer thus obtained can be used in devices of the electrooptical modulator type in guided or non-guided configuration, directional and bistable electrooptical coupler.

 The activity in non-linear optics of these materials is determined by measuring the cubic or quadratic susceptibility.

 The activity of materials in nonlinear optics is determined by the measurement of second, third or umpteenth order susceptibilities.

dans laquelle : P et Po représentent la polarisation respectivement en présence et en absence de champ électromagnétique.The susceptibilities of a material are directly related to the polarization of the material by the following fundamental relationship

in which: P and Po represent the polarization respectively in the presence and in the absence of electromagnetic field.

représentent les susceptibilités linéaires et non linéaires du matériau.E represents the electric excitation field

represent the linear and non-linear susceptibilities of the material.

 Indeed, the coefficient X 1 reflects its activity in linear optics.

 The coefficients # 2 and X represent the second and third order susceptibilities respectively.

 These susceptibilities reflect the anharmonicity of the electronic potential in the material.

 Furthermore, odd-order susceptibilities, such as susceptibility 7 (3 # 3 are never zero for all materials. On the contrary, even-order susceptibilities such as quadratic susceptibility X are zero for centrosymmetric materials .

 To assess and measure the susceptibility coefficient X of materials, it is determined by comparison with that of a reference material, for example quartz or potassium dihydrogen phosphate (KDP).

 The measurement of the susceptibility fi 2 is generally carried out at frequencies (-2 av; W, uJ) in a doubling harmonic experiment described in the article by S.K.KtJRTZ published in Quantum Electronics ed.

 H.RABIN, C.L. TANG academic Press, 1975, tome I pages 209 - 281.

It is also possible to measure X 2 at frequencies (- uJ; aJ, o) in an electrooptical experiment. For this, the film is deposited on a glass slide covered with a transparent conductive oxide (SnO2). 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. After cooling, 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 crossed at incidence i by a laser beam polarized at 45 (5 = 633 nm).

 The film is subjected to an AC voltage #V of 1 KHZ, 10 volts.

 This voltage V modulates the phase shift PI between the waves s and p by a quantity # 0 which is detected by synchronous detection.

 The details of this measure are set out in the article "Decay of the second order. Susceptibility of poled PMMA films doped with an Azo Dye".

R. Meyrueix, G. Mignani. Nice. of SPIE. Int. Soc. Opt. Eng. Paris April 24-28, 1989, Paris.

The signal ii ~ is linked to the coefficients X 113 and X 333 by the relation

with 333 2 3 X113 n is the index of the film, i the angle of incidence of the beam by the film, and
The wavelength.

 We also measure the time necessary for the polarization due to the applied electric field to disappear after its elimination. This measurement is carried out according to a method identical to that set out above. Thus, the frequency Q of the voltage #v applied to the film is varied. When this frequency is comparable to the inverse of the orientation time of the active group, an intense KERR signal at 231 is detected as explained in the work by M. DOI et al "the theory of polymers dynamics" Oxford, 1986 .

 Other objects, characteristics, details of the invention will appear more clearly in the light of the examples given below only for information.

avec 7 g d'un prépolymère polysiloxanique de poids moléculaire Mn = 975 et contenant 0,216 mole d'îsocyanate par 100 g et de formule

en présence catalytique de dilaurate dibutyl étain. Cette réaction est conduite en milieu solvant, 1-3 diméthyl-2-imidazolidinone sec, à 900C.EXAMPLE 1 Preparation of a polymer (A)
2.6 g of a diol comprising a hyperpolarizable group, of the following formula, are reacted

with 7 g of a polysiloxane prepolymer of molecular weight Mn = 975 and containing 0.216 mole of isocyanate per 100 g and of formula

in the catalytic presence of dibutyltin dilaurate. This reaction is carried out in a solvent medium, 1-3 dimethyl-2-imidazolidinone dry, at 900C.

 The mass obtained is poured into a liter of water, then filtered and washed.

1 g of a red solid is thus recovered which is soluble in many solvents such as ~ dimethylformamide, N-methylpyrrolidone,
CH2Cl2 or the like.

This amorphous polymer has a molecular weight Mn = 2560 and
Mw = 5510, and a glass transition temperature (Tg) equal to 200C.

dans laquelle n est égal à 7 et m est égal à 4.NMR, infrared spectrometry, UV analyzes confirm the following structure of the block copolymer:

where n is 7 and m is 4.

n étant égal à 5 ou 6.EXAMPLE 2 Copolymer B
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 being 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.

 The copolymer is recovered according to the method of Example 1 and has a molecular weight Mn = 930, Mw = 6480. Its structure is confirmed by spectral analyzes.

et comme polysiloxane un composé identique à celui de l'exemple 1 avec 0,177 mole de NCO par 100 g.EXAMPLE 3: Copolymer C
Example 1 is repeated, but using as hyperpolarizable diol, the compound of the following formula

and as polysiloxane a compound identical to that of Example 1 with 0.177 mole of NCO per 100 g.

 The dark red product obtained has a molecular weight in = 7090 and i ~ = 18870 and a glass transition temperature Tg equal to 200C.

EXAMPLE 4: cosolynière D
Example 3 is repeated, with the hyperpolarizable diol the following compound

The copolymer obtained has a molecular weight Mn = 12,270 g and
Mw = 23340, its structure is confirmed by spectral analyzes. It has a Tg of 100C and m is approximately 17.

EXAMPLE 5
A mixture of diols is reacted, one of which has the formula of the diol of Example 1 and therefore the other is n-butanediol with a siloxane prepolymer of the following formula

 This prepolymer contains 0.217 mole of NCO equivalent per 100 g of prepolymer.

 This reaction is carried out as in the previous examples in dry DMEU medium and in the catalytic presence of dibutyltin dilaurate.

 The product collected is a gum having a glass transition temperature equal to about 180C.

The polymer structure, confirmed by spectral analysis includes

 Its molecular weight is Mn = 3030; Mw = 5100.

 - Measurement of the optical activity of polymer A (example 1).

This polymer after shaping according to the technique of the "bar of
Meyer "in 10 m thick fiber from a 12% solution in cyclohexanone was subjected to a polarizing electric field of 30 V / pm at 22 C This field being maintained, we apply to the mass electrode alternating voltage 1 KHZ, 60 volts.

 The determination of its electrooptical activity at a wavelength of 633 nm is carried out by polarimetry according to the method described above.

 LA>, o) = 6.5 pmV-1 is obtained.

 The time for the susceptibility J 2333 to return to 0 has been determined.

 It is about 2 DS.

Claims (7)

1. Activatable material for obtaining an activity in non-linear optics, characterized in that it comprises a block copolymer constituted by elastomeric blocks and thermoplastic blocks comprising hyperpolarizable groups and in that the block copolymer has a lower glass transition temperature or equal to the ambient temperature (150C - 3O0C) and a high glass transition temperature, higher than the ambient temperature (150C 300C). 2. Material according to claim 1, characterized in that the elastomeric blocks represent at least 10% of the molecular weight of the polymer. 3. Material according to claim 1 or 2, characterized in that the elastomeric sequences consist of recurring organopolysiloxane units. 4. Material according to claim 1, 2 or 3 characterized in that the thermoplastic sequences comprise hyperpolarisable groups grafted on the chain of recurring units constituting said sequences. 5. Material according to claim 1, 2 or 3 characterized in that the thermoplastic sequences comprise hyperpolarisable groups incorporated in the chain of recurring units constituting said sequences.  VS. Material according to one of the preceding claims, characterized in that the thermoplastic blocks consist of recurring units of the polyurethane, polyether, polyamide, polyimide, polyester type. 7. Material according to one of claims 1 to 3, 5 and 6 characterized in that the sequenced copolymer is a copolymer with organopolysiloxane blocks and polyurethane blocks. 8. Material according to claim 7, characterized in that the block copolymer consists of a series of recurring polysiloxane units A or Ai, and of polyurethane recurring units B, B1, C or Ci characterized in that the recurring units have the formulas following general

  in which  - D: which may be absent, represents the group -O- or -NH  - Z represents a divalent radical carrying a polysiloxa block  pic with formula

 R representing an aliphatic or aromatic hydrocarbon radical which can be halogenated, and Y, Y ′ hydrocarbon radicals.  - G2 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-G2-NCO  - G1 a hyperpolarizable radical having a delocalized electronic distribution, and corresponding to the rest of the diol HO-GI-OH  G, G3 represent a G1 radical or a divalent hydrocarbon radical corresponding to the remainder of a diol comprising from 2 to 20 carbon atoms, and  - ni, n2 identical or different are a number between 1 and 4000, nor can be equal to 0. 9 / Material according to claim 8, characterized in that the radical G1 has the following general formula

 in which,  U represents a group comprising a delocalized electron radical Il and at least one electron acceptor group A.  R8 represents a benzene radical substituted or.not by a lower alkyl radical.  R9 represents a lower alkylene radical. 10 / Material according to claim 9, characterized in that the radical U represents the following groupings

 in which A1, A2, A3 identical or different represent hydrogen, an alkyl radical, an electron accepting radical (A), they cannot represent hydrogen and an alkyl radical.  R4, R5 represent an aliphatic radical comprising from 1 to 4 carbon atoms.  R6 represents hydrogen, a lower alkyl radical or an electron acceptor radical (A).  it, Material according to claim 2 or 3 characterized in that the electron accepting radicals (A) are chosen from the group comprising cyano or nitro radicals. 12 / Material according to one of the preceding claims, characterized in that the groups Y and Y ', which are identical or different, are alkylene, cycloalkylene, arylene, alkylarylene or arylalkylene hydrocarbon radicals, or groups comprising a heteroatom in the chain. 13 / Copolymers according to one of claims 8 to 12, characterized in that G2 represents: alkylene radicals having from 2 to 12 carbon atoms, cyclohexylene or cyclopentylene radicals, phenylene, methylphenylene or dimethylphenylene or also a group of two groups chosen from alkylene groups having from 2 to 12 carbon atoms, cyclohexylene, cyclopentylene, phenylene, methylphenylene or dimethylphenylene radicals linked together by the valence bond, an oxygen atom, an alkylene or alkylidene group having from 1 to 4 atoms of carbon. 14 / Material according to one of claims 8 to 13 characterized in that the radicals G, G3 represent a radical G1 or alkylene radicals having from 2 to 12 carbon atoms, cyclohexylene or cyclopentylene radicals, phenylene, methylphenylene or dimethylphenylene or another set 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 the valence bond, an oxygen atom, an alkylene or alkyleneidene group having 1 to 4 carbon atoms. 15 / A method for manufacturing a material according to one of claims 7 to 14 characterized in that the ratio of isocyanate functions to other antagonistic functions is between 0.9 and 0.1, preferably between 0.95 and 1 , 05. 16 / A method according to claim 15, characterized in that the copolymer is produced in two stages, a first stage of functionalization of the monomer with polysiloxane units by reaction of the compound X-Z-X 'with an OcN-G2-NCO compound, then in a second step reaction of the product obtained in the first step with a diol of formula HO-G-OH; HO-G1-OH; HO-G1-OH and optionally a diisocyanate of formula OcN-G2-CNO. 17 / A method according to claim 16, characterized in that the two aforementioned steps are carried out simultaneously. 18 / A method according to one of claims 15 to 17, characterized in that the polymerization reaction is carried out in the absence of solvent. 19 / Method according to one of claims 15 to 17, characterized in that the polymerization reaction is carried out in the presence of solvent. 20 / A method according to claim 19, characterized in that the abovementioned solvent is chosen from the group comprising halogenated hydrocarbons, tetrahydrofuran, dimethylurea, diiethylethylurea (DMEU), direthyl acetamide (DMAC), disethylforiamide, N-methylpyrrolidone <NKP).  21 / A method for producing iqaterials sequenced according to one of claims 1 to 14, active in non-linear optics, characterized in that it consists in subjecting the polymer manufactured according to one of claims 8 to 14 to an electric field or magnetic to orient the hyperpolarisable groups. 22 / Optical or electro-optical device comprising a material or a block copolymer according to one of claims 1 to 14.