Organopolysiloxanes and methods for preparing same

Abstract

The present invention concerns an organopolysiloxane (A) able to be obtained by the reaction, at a temperature of between 10 C. and 75 C., betweenat least one compound (C) chosen from the organic compounds comprising at least one alkene or alkyne functional group, at least one of the substituents of which is an acid functional group and the organic compounds comprising at least one acid functional group and at least one alkene or alkyne functional group, at least one of the substituents of which is an electron-withdrawing group; andat least one organopolysiloxane (B) chosen from the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae: (I) The present invention also concerns compositions comprising said organopolysiloxanes (A) and the uses thereof. $\left(I\right)$$\begin{array}{cc}{Y}_a{Z}_b^1{\mathrm{SiO}}_{\frac{4-\left(a+b\right)}{2}};& \left(I\mathrm{.1}\right)\\ Z_c^2{\mathrm{SiO}}_{\frac{4-c}{2}}& \left(I\mathrm{.2}\right)\end{array}$

Claims

1. An organopolysiloxane (A), comprising a filler, which may be obtained by reaction, at a temperature comprised between 10 and 75 C., between: at least one compound (C) selected from the group consisting of the organic compounds comprising at least one alkene or alkyne function for which at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function for which at least one of the substituents is an electroattractor group; and at least one organopolysiloxane (B) selected from the group consisting of the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae: $\begin{array}{cc}{Y}_a{Z}_b^1{\mathrm{SiO}}_{\frac{4-\left(a+b\right)}{2}};\mathrm{and}& \left(I\mathrm{.1}\right)\\ Z_c^2{\mathrm{SiO}}_{\frac{4-c}{2}}& \left(I\mathrm{.2}\right)\end{array}$ wherein: a=1 or 2, b=0, 1 or 2 and a+b=1, 2 or 3 c=1, 2, 3 or 4 the symbols Y, either identical or different, represent a functional group of formula (I.3):
-E-(NH-G).sub.h-(NH.sub.2).sub.i(I.3) wherein: h=0 or 1; i=0 or 1; h+i=1 or 2; E represents an aliphatic, cycloaliphatic or aromatic divalent hydrocarbon comprising from 1 to 30 carbon atoms; when it is present, G represents an aliphatic hydrocarbon radical comprising from 1 to 10 carbon atoms, monovalent when i=0 or divalent when i=1; the symbols Z.sup.1 and Z.sup.2, either identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or several unsaturations and/or one or several fluorine atoms, a hydroxyl group, or a radical-OR.sup.1 with R.sub.1 which represents a linear, cyclic or branched C.sub.1-C.sub.10 hydrocarbon radical; said polyorganosiloxane (B) comprising, per molecule, at least one siloxyl unit (I.1) bearing at least one functional group of formula (I.3), the reaction being made in the presence of a filler.

2. The organopolysiloxane (A) according to claim 1 wherein the temperature is comprised between 10 and 70 C.

3. The organopolysiloxane (A) according to claim 1, wherein the compound (C) is selected from among the organic compounds comprising at least a double carbon-carbon bond for which at least one of the substituents is a carboxylic acid function.

4. The organopolysiloxane (A) according to claim 1, wherein the compound (C) is selected from among the compounds of formula (II) ##STR00009## wherein: R.sup.2, R.sup.3 and R.sup.4, either identical or different, represent a hydrogen atom, a COOH group or a C.sub.1-C.sub.6; R.sup.5 represents a hydrogen atom, an alkyl group or an aryl group, wherein the alkyl and the aryl comprise at least one COOH group.

5. The organopolysiloxane (A) according to claim 1, wherein the compound (C) is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, 2-carboxyethylacrylate, 3-carboxypropylacrylate, maleic acid, fumaric acid, 2-(acryloyloxy)acetic acid, 2-(acryloyloxy)propanoic acid, 3-(acrylolyloxy)propanoic acid, 2-(acryloyloxy)-2-phenylacetic acid, 4-(acryloyloxy)butanoic acid, 2-(acryloyloxy)-2-methylpropanoic acid, 5-(acryloyloxy)pentanoic acid, (E)-but-2-enoic acid, (Z)-prop-1-ene-1,2,3-tricarboxylic acid, cinnamic acid, sorbic acid, 2-hexenoic acid, 2-pentenoic acid, 2,4-pentadienoic acid, ethenesulfonic acid, vinylphosphonic acid, (1-phenylvinyl)phosphonic acid, 3-(vinylsulfonyl)propanoic acid, 2-(vinylsulfonyl)acetic acid, 2-(vinylsulfonyl)succinic acid, acetylene dicarboxylic acid and propiolic acid.

6. The organopolysiloxane (A) according to claim 1, wherein the organopolysiloxane (B) is selected from the group consisting of the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae: $\begin{array}{cc}{Y}_a{Z}_b^1{\mathrm{SiO}}_{\frac{4-\left(a+b\right)}{2}};\mathrm{and}& \left(I\mathrm{.1}\right)\\ Z_c^2{\mathrm{SiO}}_{\frac{4-c}{2}}& \left(I\mathrm{.2}\right)\end{array}$ wherein: Y and Z.sup.1 and Z.sup.2 are definitions given in claim 1; a=1 or 2, b=0, 1 or 2 and a+b=2 or 3 c=1 or 2.

7. The organopolysiloxane (A) according to claim 1, characterized in that the organopolysiloxane (B) has a degree of polymerization comprised between 2 and 5,000.

8. The organopolysiloxane (A) according to claim 1, wherein the organopolysiloxane (B) has a dynamic viscosity measured at 25 C. with a rheometer with imposed stress comprised between 1 and 100,000 mPa.Math.s.

9. The organopolysiloxane (A) according to claim 1, characterized in that its viscosity, measured at 25 C. with a rheometer with imposed stress, is at least 10 times greater than that of the organopolysiloxane (B).

10. A method for preparing an organopolysiloxane (A) comprising putting into contact at a temperature comprised between 10 and 75 C.: at least one compound (C) selected from the group consisting of the organic compounds comprising at least one alkene or alkyne function for which at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function for which at least one of the substituents is an electronattractor group; and at least an acid function, and at least one organopolysiloxane (B) selected from the group consisting of the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae: $\begin{array}{cc}{Y}_a{Z}_b^1{\mathrm{SiO}}_{\frac{4-\left(a+b\right)}{2}};\mathrm{and}& \left(I\mathrm{.1}\right)\\ Z_c^2{\mathrm{SiO}}_{\frac{4-c}{2}}& \left(I\mathrm{.2}\right)\end{array}$ wherein: a=1 or 2, b=0, 1 or 2 and a+b=1, 2 or 3 c=1, 2, 3 or 4 the symbols Y, either identical or different, represent a functional group of formula (I.3):
-E-(NH-G).sub.h-(NH.sub.2).sub.i(I.3) wherein: h=0 or 1; i=0 or 1; h+i=1 or 2; E represents an aliphatic, cycloaliphatic or aromatic divalent hydrocarbon radical comprising from 1 to 30 carbon atoms; when it is present, G represents an aliphatic hydrocarbon radical comprising from 1 to 10 carbon atoms, monovalent when i=0 or divalent when i=1; the symbols Z.sup.1 and Z.sup.2, either identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or several unsaturations and/or one or several fluorine atoms, a hydroxyl group, or a radical-OR.sup.1 with IV which represents a linear, cyclic or branched C.sub.1-C.sub.10 hydrocarbon radical; said polyorganosiloxane (B) comprising, per molecule at least one siloxyl unit (I.1) bearing at least one functional group of formula (I.3), the method being carried out in the presence of a filler.

11. The method according to claim 10, applied at a temperature comprised between 10 and 70 C.

12. The method according to claim 10, applied in bulk or in the presence of a solvent.

13. The method according to claim 10, wherein the obtained organopolysiloxane (A) has a dynamic viscosity, measured at 25 C. with a rheometer with imposed stress, at least 10 times greater than that of the organopolysiloxane (B).

14. The method according to claim 10, wherein the ratio r representing the ratio between the number of moles of alkene or alkyne function of the compound (C) for which at least one of the substituents is an electroattractor group or an acid function, and the number of moles of NH bonds borne by the organopolysiloxane (B) $r=\frac{n\left(\text{C=C}\mathrm{ou}\text{CC}\right)}{n\left(\text{NH}\right)}$ is comprised between 0.01 and 10.

15. The method according to claim 10, wherein the ratio J representing the ratio between the number of mole of acid functions of the compound (C) and the number of mole of the amine function of the organopolysiloxane (B) $l=\frac{\begin{array}{c}\mathrm{number}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{the}\mathrm{compound}\left(C\right)\\ \mathrm{number}\mathrm{of}\mathrm{acid}\mathrm{functions}\mathrm{of}\mathrm{the}\mathrm{compound}\left(C\right)\end{array}}{\begin{array}{c}\mathrm{number}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{the}\mathrm{compound}\left(B\right)\\ \mathrm{number}\mathrm{of}a\mathrm{mine}\mathrm{functions}\mathrm{of}\mathrm{the}\mathrm{compound}\left(B\right)\end{array}}$ is comprised between 0.01 and 20.

16. A composition K1 comprising at least one organopolysiloxane (A) according to claim 1, and at least one filler and optionally at least one other organopolysiloxane and/or one or several usual functional additives, and/or an organopolysiloxane comprising at least one carboxylic function and/or at least one organopolysiloxane (B) as defined in claim 1.

17. The use of A method of using at least one organopolysiloxane (A) according to claim 1, comprising using said at least one organopolysiloxane in wound care; for the encapsulation of electronic components; as coatings; as additives; for temporary printing, or for thin layer coating.

18. A method of using at least one organopolysiloxane (A) according to claim 1, comprising using said at least one organopolysiloxane in paints, coatings, adhesives, sealants, personal care, health care, textile treatment, electronics, automotive field, rubbers, or anti-foam compositions.

19. A composition X for the preparation of an organopolysiloxane (A) according to claim 1, comprising: at least one compound (C) selected from the group consisting of the organic compounds comprising at least one alkene or alkyne function for which at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function for which at least one of the substituents is an electroattractor group; and at least one organopolysiloxane (B) selected from the group consisting of the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae: $\begin{array}{cc}{Y}_a{Z}_b^1{\mathrm{SiO}}_{\frac{4-\left(a+b\right)}{2}};\mathrm{and}& \left(I\mathrm{.1}\right)\\ Z_c^2{\mathrm{SiO}}_{\frac{4-c}{2}}& \left(I\mathrm{.2}\right)\end{array}$ wherein: a=1 or 2, b=0, 1 or 2 and a+b=1, 2 or 3 c=1, 2, 3 or 4 the symbols Y, either identical or different, represent a functional group of formula (I.3):
-E-(NH-G).sub.h-(NH.sub.2).sub.i(I.3) wherein: h=0 or 1; i=0 or 1; h+i=1 or 2; E represents an aliphatic, cycloaliphatic or aromatic divalent hydrocarbon radical comprising from 1 to 30 carbon atoms; when it is present, G represents an aliphatic hydrocarbon radical comprising from 1 to 10 carbon atoms, monovalent when i=0 or divalent when i=1; the symbols Z.sup.1 and Z.sup.2, either identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or several unsaturations and/or one or several fluorine atoms, a hydroxyl group, or a radical-OR.sup.1 with IV which represents a linear, cyclic or branched C.sub.1-C.sub.10 hydrocarbon radical; said polyorganosiloxane (B) comprising, per molecule, at least one siloxyl unit (I.1) bearing at least one functional group of formula (I.3).

20. The organopolysiloxane (A) according to claim 1, wherein the filler is a mineral filler.

21. The organopolysiloxane (A) according to claim 10, wherein the filler is a mineral filler.

Description

EXAMPLES

(1) In the examples below, given as an illustration, reference is made to the following definitions: Mn represents the number average molar mass. PDMS=polydimethylsiloxane.

(2) The PDMSes applied in the following examples fit one of the following formulae:

(3) ##STR00006## ORGANOSILOXANE (1):

N-(2-aminoethyl)-3-aminopropylmethylbis(trimethylsiloxy)silane

(4) ##STR00007## ORGANOSILOXANE (2): Commercial, Gelest SIA0604.5

3-aminopropylmethylbis(trimethylsiloxy)silane

(5) ##STR00008## PDMS(3): Gelest, Mn3000 g/mol; compound of formula (III); amount of NH bonds per gram=1.33.Math.10.sup.3 mol/g; PDMS(4): Gelest; a compound of formula (III) amount of NH bond per gram=8.0.Math.10.sup.5 mol/g; Mn50000 g/mol PDMS(5): Gelest; compound of formula (III) Mn30000 g/mol; amount of NH bonds per gram=1.33.Math.10.sup.4 mol/g PDMS(6): Gelest; compound of formula (IV) amount of NH bond per gram=1.71.Math.10.sup.3 mol/g; PDMS(7): Gelest; compound of formula (IV); amount of NH bond per gram=2.43.Math.10.sup.3 mol/g; PDMS(8): Gelest; compound of formula (IV); amount of NH bond per gram=5.14.Math.10.sup.3 mol/g; PDMS(9): Gelest; compound of formula (V); amount of NH bond per gram=6.54.Math.10.sup.3 mol/g; PDMS(10): Gelest; compound of formula (V); amount of NH bond per gram=8.57.Math.10.sup.4 mol/g; PDMS(11): Bluestar Silicones; compound of formula (V) amount of NH bond per gram=3.21.Math.10.sup.4 mol/g; PDMS(12): Bluestar Silicones; compound of formula (V) with terminal units of dimethylmethoxysilyl instead of trimethylsilyl, amount of NH bond per gram=1.61.Math.10.sup.4 mol/g
Dynamic Viscosity:

(6) The dynamic viscosity of the products was measured by means of a rheometer with imposed stress (TA-DHRII). The measurements were conducted in a flow mode with a cone/plane geometry with a diameter of 40 mm and having a truncation of 52 m. The viscosity was recorded according to the shearing rate (0.01-100 s.sup.1) at 25 C.

(7) NMR:

(8) The nuclear magnetic resonance spectra .sup.1H (NMR) were recorded on a spectrometer Bruker Avance III at 400 MHz. The samples were dissolved ether in deuterated chloroform, or in a CDCl.sub.3/MeOD mixture (60/40 mol) and analyzed at 27 C.

(9) Rheology:

(10) Rheological analyses were conducted by means of a rheometer with imposed stress (TA-DHRII) at 25 C. by using a plane/plane geometry (diameter of 40 mm). The frequency sweeps were recorded in the linear viscoelastic domain of the products between 100 and 0.01 Hz.

Example 1: Preparation of the ORGANOSILOXANE (1)

(11) THE ORGANOSILOXANE (1) was prepared according to the following procedure: N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (5.0 g) and hexamethyldisiloxane (20.1 g) were mixed in a two-necked flask surmounted with a condenser in the presence of tetramethylammonium hydroxide dissolved in methanol (0.5 g). The reaction mixture was stirred with nitrogen sweeping at room temperature for 10 minutes and then was heated to 90 C. for 2 hours and then to 130 C. for 30 minutes. The reaction mixture was then cooled down to room temperature (20 to 25 C.) and the obtained product was purified by fractionated vacuum distillation. A fraction of 2.3 g corresponding to the ORGANOSILOXANE (1) is taken out at 106 C. at 0.41 mbars at the column head, the boiler being brought to 200 C. The yield of the reaction is 30%.

Example 2: Reaction of the ORGANOSILOXANE (1) with Acrylic Acid

(12) In a two-necked flask, are mixed the ORGANOSILOXANE (1) and the acrylic acid. The ORGANOSILOXANE (1) and the acrylic acid are added in amounts such that r=0.33 and J=0.5. The mixture is put under magnetic stirring for 24 h at 50 C. at atmospheric pressure.

(13) An .sup.1H NMR analysis of the reaction medium sampled at 1, 4, 6, 8 and 24 h of reaction, gave the possibility of showing a disappearance of the acrylic functions over time. Without intending to be bound by any theory, this disappearance of the acrylic functions is due to the Aza-Michael reaction between the NH bonds of the ORGANOSILOXANE (1) and the acrylic functions.

(14) A test 3 was also carried out, identical with the test 2 (same proportion) but by replacing the ORGANOSILOXANE (1) by octamethyltrisiloxane. This test did not show the formation of a polymer of acrylic acid. This shows that the disappearance of the acrylic functions observed by NMR in test 2 is not due to a polymerization reaction of acrylic acid but actually to the Aza-Michael reaction between the NH bonds borne by the ORGANOSILOXANE (1) and the double carbon-carbon bond of the acrylic acid.

Example 3: Influence of the Temperature on the Conversion of the Acrylic Acid

(15) In three sealed pill boxes were mixed the ORGANOSILOXANE (2) and the acrylic acid (r=0.5, J=1). The reaction mixtures are maintained at a temperature of 25 C. (Test 5), 50 C. (Test 6) and 70 C. (Test 7). The conversion of the acrylic functions over time was followed with .sup.1H NMR. The results are shown in the following table 1.

(16) TABLE-US-00001 TABLE 1 TEST No. 5 6 7 Time (h) Conversion (%) 0 0 0 0 1 16 39 84 2 18 54 / 4 23 71 98 6 27 81 / 7 / / 100 8 32 86 / 24 55 98 / 48 73 100 / 49 / / 100 168 94 100 /

(17) These results show that by increasing the temperature it is possible to obtain a total conversion of the acrylic functions for 7 h at 70 C.

(18) The obtained products were qualitatively analyzed in terms of viscosity, homogeneity, solubility, etc. The results show that the obtained products are homogeneous, soluble in chloroform, dispersible in water, more viscous than the initial ORGANOSILOXANE (2) and have a transparency equivalent to that of the initial ORGANOSILOXANE (2).

Example 4: Reaction of PDMS (3) with Bulk Acrylic Acid

(19) In a one-neck flask of 15 mL, were mixed the PDMS (3) and the acrylic acid. The PDMS (3) and the acrylic acid are added in amounts such that r=0.5 and J=1. The reaction mixture was set with magnetic stirring for 72 h at a temperature of 50 C. No post-reaction treatment was applied. A .sup.1H NMR analysis of the obtained product in CDCl.sub.3 at 27 C. (128 scans) gave the possibility of showing a disappearance of the acrylic functions. The conversion was calculated, on the basis of .sup.1H NMR, at 96%, at t=72 h.

(20) The dynamic viscosities of PDMS (3), of the mixture PDMS (3) and the acrylic acid at t=0, and of the product obtained after 72 h of reaction were measured with different shear rates (0.1-100 s.sup.1) and are shown in the table 2 hereafter.

(21) TABLE-US-00002 TABLE 2 Dynamic viscosity TEST No. Products (mPa .Math. s) 8 PDMS (3) .sup.57.5 6.5 9 PDMS (3)/AA t = 0 1225 50 9 PDMS (3)/AA t = 72 h 1.75 .Math. 10.sup.5 5 .Math. 10.sup.3

(22) These results show that the PDMS (3) initially has a low viscosity. The dynamic viscosity increases when the PDMS (3) is mixed with acrylic acid at t=0. Without intending to be bound by any theory, this increase in dynamic viscosity is due to the acid-base reaction between the amine functions of PDMS (3) and acrylic acid. The dynamic viscosity of the final product (product stemming from the Aza-Michael reaction between the PDMS (3) and acrylic acid after 72 h) is more than 100 times greater than that of the PDMS (3) and much greater than that of the mixture of PDMS (3) and acrylic acid at t=0. Without intending to be bound by any theory, and as shown by the results of Example 3, this increase in dynamic viscosity is due to the Aza-Michael reaction coupled with an acid-base reaction between the PDMS (3) and the acrylic acid.

Example 5: Variation in the Nature of the PDMS, of J and r

(23) The PDMSes 4 to 11 and the acrylic acid were reacted in bulk, in the ratios described in the table 4 hereafter, in a suitable plastic container. The reaction mixture was homogenized by means of a planetary gear mixer at a high speed (2,750 revolutions per minute) for 2 minutes and 30 seconds. An exothermal reaction is visible during the homogeneization, this is why the products were cooled to 20 C. before being homogenized. Thus, the maximum temperature within the product does not exceed 25 C. After homogeneization, the products are left at room temperature for several days (>17 days). The reaction conditions for the different tests are gathered in the following table 3.

(24) TABLE-US-00003 TABLE 3 TEST No. PDMS r J 10 PDMS (4) 0.52 1 11 PDMS (5) 0.54 1 12 PDMS (6) 0.50 1 13 PDMS (7) 0.51 1 14 PDMS (8) 0.50 1 15 PDMS (9) 0.67 1 16 PDMS (10) 0.68 1 17 PDMS (10) 1.35 2 18 PDMS (11) 0.71 1

(25) The obtained products were analyzed by .sup.1H NMR after 17 days of reaction at room temperature (20-25 C.) which gave the possibility of calculating the conversion of the acrylic functions. The obtained products were also evaluated in terms of viscosity (visual observation) and of solubility in different solvents. The results of these analyses are grouped in the table 4 hereafter.

(26) TABLE-US-00004 TABLE 4 Solubility (10 g/L) TEST No. Conversion (%) CDCl.sub.3 H.sub.2O IPA THF MCH 10 67 S 11 68 S 12 72 S 13 70 S 14 I D D 15 I I I I I 16 87 S I S S 17 84 S I S S 18 90 S I S S
Captions: S: soluble; I: insoluble; D: dispersible; : non-tested CDCl.sub.3: deuterated chloroform; H.sub.2O: water; IPA: Isopropanol; THF: Tetrahydrofurane, MCH: Methylcyclohexane.

(27) The obtained products all have a viscosity at least 10 times greater than the respective initial PDMSes. A high conversion rate of the acrylic functions after 17 days was determined by .sup.1H NMR for all the products which may be solubilized in deuterated chloroform. The variation in the nature of the PDMS and of the ratios r and J therefore give the possibility of adjusting the properties of the synthesized materials.

(28) The viscoelastic properties of the products obtained for the tests 16, 17 and 18 were recorded by means of a rheometer with imposed stress. The initial viscoelastic properties of the PDMSes (10) and PDMS (11) were also measured. For this, the time-dependent change in the elastic (G) and viscous (G) moduli versus frequency was recorded in the following conditions:

(29) Deformation () of 0.1% applied for the test 16 and the PDMS (10), deformation (6) of 0.03% applied for the test 17 and deformation () of 0.2% applied for the test 18 and the PDMS (11).

(30) The results obtained after 18 days of reaction are grouped in both following tables 5 and 6.

(31) TABLE-US-00005 TABLE 5 TEST No. PDMS (10) 16 17 Frequency (Hz) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) 100 3.6 .Math. 10.sup.2 1.7 .Math. 10.sup.2 2.2 .Math. 10.sup.5 3.9 .Math. 10.sup.4 2.6 .Math. 10.sup.5 4.9 .Math. 10.sup.4 10 7 45 1.7 .Math. 10.sup.5 4.8 .Math. 10.sup.4 1.9 .Math. 10.sup.5 4.2 .Math. 10.sup.4 1 1.3 5 8.3 .Math. 10.sup.4 5.3 .Math. 10.sup.4 1.2 .Math. 10.sup.5 5.3 .Math. 10.sup.4 0.1 1.1 0.5 1.9 .Math. 10.sup.4 2.6 .Math. 10.sup.4 3.9 .Math. 10.sup.4 4.2 .Math. 10.sup.4 0.01 / / 1.3 .Math. 10.sup.3 5.7 .Math. 10.sup.3 4.8 .Math. 10.sup.3 1.1 .Math. 10.sup.4 Crossing G/G Crossing G/G Crossing G/G Frequency (Hz) > 100 0.2 0.1

(32) TABLE-US-00006 TABLE 6 TEST No. PDMS (11) 18 Frequency (Hz) G (Pa) G (Pa) G (Pa) G (Pa) 100 2.1 .Math. 10.sup.3 4.2 .Math. 10.sup.3 1.2 .Math. 10.sup.5 1.8 .Math. 10.sup.4 10 1.4 .Math. 10.sup.2 6.5 .Math. 10.sup.2 9.6 .Math. 10.sup.4 2.6 .Math. 10.sup.4 1 4 76 4.9 .Math. 10.sup.4 2.8 .Math. 10.sup.4 0.1 0.2 8 1.7 .Math. 10.sup.4 1.5 .Math. 10.sup.4 0.01 0.2 0.9 3.4 .Math. 10.sup.3 5.3 .Math. 10.sup.3 Crossing G/G Crossing G/G Frequency (Hz) >100 0.6

(33) The results show that the crossing point G/G is at 0.2 Hz for test 16, at 0.1 Hz for test 17 and at 0.6 Hz for test 18. The three obtained products therefore behave as viscoelastic solids over a wide range of frequencies.

(34) The results also show an increase in the viscosity of the products obtained in tests 16 and 17 relatively to PDMS (10) and in test 18 relatively to PDMS (11), this increase being due to the Aza-Michael reaction coupled with the acid-base reaction.

(35) From these results it was able to be inferred, by calculation, the following complex viscosities shown in table 7 and 8.

(36) TABLE-US-00007 TABLE 7 TEST No. PDMS (10) 16 17 Frequency (Hz) * (Pa .Math. s) 100 0.6 3.5 .Math. 10.sup.2 4.2 .Math. 10.sup.2 10 0.7 2.8 .Math. 10.sup.3 3.1 .Math. 10.sup.3 1 0.8 1.6 .Math. 10.sup.4 2.2 .Math. 10.sup.4 0.1 1.9 5.2 .Math. 10.sup.4 9.1 .Math. 10.sup.4 0.01 / 9.3 .Math. 10.sup.4 2.0 .Math. 10.sup.5

(37) TABLE-US-00008 TABLE 8 TEST No. PDMS (11) 18 Frequency (Hz) * (Pa .Math. s) 100 7 2.0 .Math. 10.sup.2 10 11 1.6 .Math. 10.sup.3 1 12 9.0 .Math. 10.sup.3 .,1 13 3.6 .Math. 10.sup.4 0.01 15 1.0 .Math. 10.sup.5

(38) The results show a decrease in the complex viscosity when the frequency increases.

Example 6: Reaction of the PDMS (3) with Acrylic Acid in the Presence of a Solvent (25 C.)

(39) In an one-neck flask of 25 mL, are mixed the PDMS (3), the isopropanol (IPA, 33% by weight based on the total weight of PDMS (3) and of acrylic acid) and acrylic acid. The PDMS (3) and the acrylic acid are added in amounts such that r=0.5 and J=1. The reaction mixture is set under magnetic stirring at 25 C. for 7 days. A .sup.1H NMR analysis of the obtained product in CDCl.sub.3 at 27 C. (128 scans) gave the possibility of showing the disappearance of the acrylic functions. At t=42 h, the conversion was estimated on the basis of .sup.1H NMR as 37%.

Example 7: Influence of the Solvent (50 C.)

(40) The reaction set into play PDMS (3) and the acrylic acid used in Examples 5 and 7 in the same proportions (r=0.5, J=1). To the reaction medium, is either added or not a solvent (85 mol-%): tert-butanol, isopropanol/water solution (50/50 mol) or a saturated solution of ammonia/isopropanol and the mixture is set under magnetic stirring at 50 C. for 24 h. The conversion of the acrylic functions is followed by .sup.1H NMR and the results are shown in table 9 below.

(41) TABLE-US-00009 TABLE 9 Conversion (%) versus time (h) TEST No. Reaction medium 0 h 1 h 4 h 8 h 24 h 9 Bulk 0 8 17 31 69 19 Tert-Butanol 0 5 12 25 64 20 IPA/Water 0 0 3 5 35 21 Ammonia solution 0 8 18 / 56

(42) These data show, in combination with the results of Examples 2, 4 and 6, that the method of the invention may be applied in the presence of different solvents or in bulk.

Example 8: Reaction of the ORGANOSILOXANE (2) with 2-carboxyethylacrylate

(43) In a sealed pill box, were mixed the ORGANOSILOXANE (2) and 2-carboxyethylacrylate in proportions such that r=0.5 and J=1. The mixture is put under magnetic stirring for 48 h at 50 C. at atmospheric pressure. A .sup.1H NMR analysis of the reaction medium sampled at 1, 4, 7, 24 and 48 h of reaction, gave the possibility of showing a disappearance of the acrylic functions over time. Without intending to be bound by any theory, this disappearance of the acrylic functions is due to the Aza-Michael reaction between the NH bonds of the ORGANOSILOXANE (2) and the acrylate functions. At t=48 h, a conversion of the acrylate functions by a value of 96% is attained. The table 10 below groups the data in terms of conversion relatively to the reaction time.

(44) TABLE-US-00010 TABLE 10 Time (h) Conversion (%) 1 62 4 73 6.5 77 24 90 48 96

Example 9: Effect of the Temperature of the Method. Reaction Between an Organopolysiloxane (PDMS 12) and Itaconic Acid

(45) The PDMS (12) is an organopolysiloxane of the same overall formula as the compound (V) but with terminal units of dimethylmethoxysilyl instead of trimethylsilyl, and having an amount of NH bonds per gram of 1.61.Math.10.sup.4 mol/g.

(46) Two reactions are applied, one at 50 C. according to the invention and one at 120 C. (comparative test). Itaconic acid is a solid which is not soluble in the PDMS (12) at room temperature (20-30 C.). It was solubilized beforehand in methanol.

Example 9-a

(47) 0.11 g of solubilized itaconic acid in 0.23 g of methanol, i.e. 0.008 moles of itaconic acid which corresponds to 0.0016 moles of acid function, were mixed with 15.00 g of PDMS (12) as described above, which corresponds to 0.0024 mol of NH bonds and 0.0016 mol of amine functions. The PDMS (12) was cooled beforehand below 0 C. before adding the solubilized itaconic acid. The mixture was then homogenized by means of a planetary gear mixer for 5 minutes at 2,750 revolutions per minute, the maximum temperature within the mixture not exceeding 25 C. After homogeneization, the mixture was placed in the oven at a temperature of 50 C. for one week so that the Aza-Michael reaction takes place and that the methanol is gradually evaporated.

(48) The obtained product is colorless, transparent, homogeneous and soluble in THF and in methylcyclohexane.

Example 9-b

(49) 0.11 g of solubilized itaconic acid in 0.23 g of methanol, i.e. 0.008 mol of itaconic acid which corresponds to 0.0016 moles of acid function, were mixed with 15.00 g of PDMS (12) as described above, which corresponds to 0.0024 mole of NH bond and 0.0016 mole of amine functions. The reaction medium is placed for 4 h at 120 C. in a one-neck flask surmounted with a condenser.

(50) The obtained product is slightly yellowish and is not soluble in THF, nor in methylcyclohexane.

(51) Both obtained products did not have the same properties which shows that they are different.

Example 10: Synthesis of a Supramolecular Material

(52) 0.77 g of acrylic acid, i.e. 0.011 moles of acid function, were mixed with 100 g of PDMS (12) cooled beforehand to 20 C., with a structure as described in Example 10, which corresponds to 0.0161 mol of NH bonds and 0.011 mol of amine functions (r=0.68 and J=1). The mixture was then homogenized by means of a planetary gear mixer for 5 minutes at 2,750 rpm, the maximum temperature within the mixture not exceeding 25 C. After homogeneization, the mixture was placed in the oven in a hermetic flask at a temperature of 50 C. for one week.

(53) The obtained product is a transparent viscoelastic solid. This product swells in THF and methylcyclohexane. After adding a chaotrope agent (<1% by mass) which gives the possibility of breaking the ionic bonds within the material, the product is totally soluble thereby showing its supramolecular nature.

(54) The obtained supramolecular product was also transformed as a film with a thickness of 1 mm under pressure for 48 h at 50 C. Specimens of the H3 type (L.sub.0=17 mm, thickness of 1 mm, width=4 mm according to the ISO 37:2011 standard) are cut out by dye-stamping and are left for one day at 45%5% of humidity and at 25 C.1 C. Uniaxial tensile tests or cyclic tensile tests were carried out with a tensile machine MTS 2/m with a sensor of 10N and a drawing speed of 0.25 s.sup.1. The dependency of the mechanical properties with the drawing speed was achieved by varying the drawing speed from 0.08 s-1 to 0.42 s-1. The obtained tensile strength is around 0.2 MPa and the elongation at break is extremely high, of the order of 4,000%.

Example 11: Synthesis of a Charged Supramolecular Material

(55) Example 10 was again conducted as described earlier. Directly after homogeneization of both compounds by means of a planetary mixer, 5% by weight of a hydrophobic pyrogenated silica (Aerosil R104) was added and this mixture is again homogenized by means of the planetary gear mixer for 10 minutes at 2,750 rpm and then placed in the oven in a hermetic flacon at a temperature of 50 C. for one week.

(56) As described earlier, specimens H3 were cut out from the obtained product, put in the form of a film beforehand. Tensile tests were carried out like in Example 11. The tensile strength is 0.5 MPa and the elongation at break is always very high, of the order of 2,000%.