Curable Composition Comprising Polysiloxane Polyalkyleneglycol Brush Copolymers

Abstract

The invention relates to a curable composition comprising: a) at least one polymer having at least one silicon-containing group of formula —Si(R.sup.1).sub.k(Y).sub.3-k as defined herein, and b) at least one hydroxyl-functionalized polysiloxane polyalkyleneglycol brush copolymer of the structure [A(-X—B)].sub.s as defined herein; and an adhesive, sealant, or coating material comprising said curable composition and use thereof.

Claims

1. A curable composition, comprising: a) at least one polymer having at least one silicon-containing group of Formula (A)
—Si(R.sup.1).sub.k(Y).sub.3-k  (A), wherein each R.sup.1 is independently selected from a hydrocarbon radical containing 1 to 20 C atoms or a triorganosiloxane group of formula —O—Si(R.sup.2).sub.3, wherein each R.sup.2 is independently selected from a hydrocarbon radical containing 1 to 20 C atoms; each Y is independently selected from a hydroxy group or a hydrolysable group; and k is 0, 1 or 2; b) at least one hydroxyl-functionalized polysiloxane polyalkyleneglycol brush copolymer of the structure [A(-X—B)].sub.s, wherein A represents said polysiloxane backbone; B represents said polyalkyleneglycol side chain; X is a linker group characterized by including the moiety Si—C—C— of which said Si is a part of the polysiloxane backbone A; and s is an integer of from 1 to 100.

2. The curable composition according to claim 1, wherein the polymer a) has a polymer backbone that is selected from alkyd resins, (meth)acrylate polymers and (meth)acrylamide polymers and the salts thereof, phenolic resins, polyalkylenes, polyamides, polycarbonates, polyols, polyethers, polyesters, polyurethanes, vinyl polymers, polysiloxanes, and copolymers composed of at least two of the above-mentioned polymer classes.

3. The curable composition according to claim 1, wherein said hydroxyl-functionalized polysiloxane polyalkyleneglycol brush copolymer has the number average molecular weight (Mn) of from 1000 to 200,000 g/mol.

4. The curable composition according to claim 1, wherein the hydroxyl-functionalized polysiloxane polyalkyleneglycol brush copolymer is represented by Formula (I) ##STR00010## wherein: Z is a covalent bond or selected from a polyoxyalkylene having a molecular weight of less than 10000 g/mol or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same or different and are independently selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom, wherein R.sup.3, R.sup.4 and R.sup.5 may be independently selected in each unit n1, n2, n3, and p; R.sup.12 is selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.7 is selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.8, R.sup.9, R.sup.10 and R.sup.11 may be the same or different and in each unit m they are independently selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; n1 and n2 is an integer independently selected from 0 to 1000, with the proviso that not both of n1 and n2 are 0; n3 is an integer from 0 to 1000; p is an integer from 0 to 1000; and m is an integer from 1 to 1500.

5. The curable composition according to claim 4, wherein in Formula (I): Z is selected from a C.sub.1-C.sub.20 alkylene group, a C.sub.6-C.sub.18 arylene group or a C.sub.6-C.sub.18 aralkylene group, which may contain at least one heteroatom; and/or R.sup.7 is selected from a C.sub.1-C.sub.12 alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.6-C.sub.18 aryl group or a C.sub.6-C.sub.18 aralkyl group, which may contain at least one heteroatom; and/or R.sup.12 is CR.sup.a.sub.2 where each R.sup.a may be the same or different and is independently selected from hydrogen, a C.sub.1-C.sub.12 alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.6-C.sub.18 aryl group or a C.sub.6-C.sub.18 aralkyl group, which may contain at least one heteroatom.

6. The curable composition according to claim 4, wherein in Formula (I): Z is selected from a C.sub.1-C.sub.20 alkylene group which may contain at least one heteroatom; and/or R.sup.7 is selected from a C.sub.1-C.sub.8 alkyl group, more preferably a methyl group; and/or R.sup.12 is CR.sup.a.sub.2 where both R.sup.a are hydrogen.

7. The curable composition according to claim 4, wherein in Formula (I) each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently selected from a C.sub.1-C.sub.12 alkyl group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.6-C.sub.18 aryl group or a C.sub.6-C.sub.18 aralkyl group, which may contain at least one heteroatom.

8. The curable composition according to claim 4, wherein in Formula (I) each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently selected from a C.sub.1-C.sub.8 alkyl group or a C.sub.6-C.sub.18 aryl group, either of which may contain at least one heteroatom.

9. The curable composition according to claim 4, wherein in Formula (I) R.sup.8, R.sup.9 and R.sup.11 are hydrogen; and R.sup.10 is either a phenyl group or a C.sub.1-C.sub.8 alkyl group.

10. The curable composition according to claim 1, wherein the hydroxyl-functionalized polysiloxane polyalkyleneglycol brush copolymer is obtained by a method comprising the steps of: a) reacting a hydroxyalkyl allyl ether having a primary or secondary alcohol group with a polyhydridosiloxane under anhydrous conditions and under catalysis of a transition metal catalyst of which the transition metal is selected from Groups 8 to 10 of the Periodic Table to provide a hydroxyl-functionalized polysiloxane prepolymer having Formula (II), ##STR00011## wherein: Z is a covalent bond or selected from a polyoxyalkylene having a molecular weight of less than 10000 g/mol or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same or different and are independently selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.12 is selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.7 is selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; n1 and n2 is an integer independently selected from 0 to 1000, with the proviso that not both of n1 and n2 are 0; n3 is an integer from 0 to 1000; and p is an integer from 0 to 1000, said hydroxyalkyl allyl ether conforming to Formula (IV), and ##STR00012## wherein Z, R.sup.12 and R.sup.7 are as defined above, said polyhydridosiloxane conforming to Formula (V) ##STR00013## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and p are as defined above; and n is n1+n2+n3, b) in the presence of the obtained hydroxyl-functionalized polysiloxane prepolymer of Formula (II) and a catalyst, performing a ring-opening polymerization of at least one alkylene oxide monomer having Formula (III): c) ##STR00014## wherein: each R.sup.8, R.sup.9, R.sup.10 and R.sup.11 may be the same or different and are independently selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom.

11. The curable composition according to claim 1, wherein the hydroxyl-functionalized polysiloxane polyalkyleneglycol brush copolymer is obtained by a method comprising the step of reacting a hydroxyalkyl allyl ether having a primary, secondary or tertiary alcohol group of Formula (VI) with a polyhydridosiloxane of Formula (V) under anhydrous conditions and under catalysis of a transition metal catalyst of which the transition metal is selected from Groups 8 to 10 of the Periodic Table, ##STR00015## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same or different and are independently selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.7 is selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; each of R.sup.8, R.sup.9, R.sup.10 and R.sup.11 may be the same or different and are independently selected from hydrogen or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; R.sup.12 is selected from a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; Z is a covalent bond or selected from a polyoxyalkylene having a molecular weight of less than 10000 g/mol or a linear, branched or cyclic hydrocarbon residue having 1 to 20 carbon atoms which may contain at least one heteroatom; m is an integer from 1 to 1500; n1 and n2 is an integer independently selected from 0 to 1000, with the proviso that not both of n1 and n2 are 0; n3 is an integer from 0 to 1000; n is n1+n2+n3; and p is an integer from 0 to 1000,

12. The curable composition according to claim 1, wherein the composition further comprises as compound c) an aminosilane.

13. The curable composition according to claim 1, wherein the composition further comprises as compound c) an aminosilane selected from the group consisting of bis(trimethylsilyl)amine, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, bis[(3-triethoxysilyl)propyl]amine, bis[(3-trimethoxysilyl)propyl]amine, aminopropylmethyldiethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, phenylaminomethyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, 3(N-phenylamino)propyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, and combinations of two or more of the above-mentioned compounds.

14. The curable composition according to claim 1, wherein the curable composition additionally contains at least one compound selected from plasticizers, stabilizers, fillers, reactive diluents, drying agents, adhesion promoters, UV stabilizers, rheological aids, solvents, and mixtures thereof.

15. An adhesive, sealant, or coating material comprising the curable composition according to claim 1.

Description

EXAMPLES

Example 1: Preparation of 1-(allyloxy)propan-2-ol

[0182] ##STR00007##

[0183] In a 1 L autoclave equipped with dosage system, 637.5 g (10.98 mol) of allyl alcohol were placed. Under argon flow, Na (2.9% mol) was added into the vessel. The mixture was stirred at room temperature until the gas evolution ceased. Then the autoclave was closed and heated until 110° C. In the next step PO was dosed (520 ml, dosage rate 1.25 g/min). After the completion of the addition of PO it was allowed to cool to room temperature and the reaction mixture was stirred overnight. A yellow transparent mixture was obtained. The mixture was neutralized using HCl (solution 37% in water) and dried with Na.sub.2SO.sub.4. The mixture was filtrated trough celite and distilled under vacuum (100 mbar, 85-95° C.). The product was obtained with good yield (70-75%) and the structure was confirmed by NMR spectroscopy and mass spectrometry.

Example 2: Preparation of (3-(2-hydroxypropoxy)propyl)methylsiloxane-co-polydimethylsiloxane

[0184] ##STR00008##

[0185] A 50 ml two neck round bottomed flask was degassed under high vacuum (1-3 mbar) and flushed with argon. Then, 8.3 mg of Pt supported on charcoal (10% of Pt in the catalyst, 0.5% mol in the mixture) and toluene (10 ml, dried over molecular sieves) were added into the flask under argon atmosphere and stirred at room temperature (20° C.) for a couple of minutes. Then 1-(allyloxy)propan-2-ol (the product from example 1; 0.72 ml) was added into the system. Polyhydridomethylsiloxane-co-polydimethylsiloxane (2.5 g, Mn 2900 g/mol) were added dropwise. The mixture was stirred and refluxed (oil bath temperature: 120° C.) under inert atmosphere (Ar) until complete conversion of the Si—H groups was achieved (the reaction was followed by .sup.1H-NMR). The mixture (when necessary) was decolorized by adding activated carbon and an excess of pentane and stirred for 16 h at room temperature. The crude was filtrated trough celite, and the solvents and volatiles were evaporated under vacuum. The obtained product (yield 55-65%) was a colorless, transparent viscous liquid. The molecular weight and structure of the product was confirmed by GPC and NMR spectroscopy. No traces of Pt were detectable in the mixture (by ICP).

Example 3: Preparation of Polydimethylsiloxane-graft-poly(propylene Oxide)

[0186] ##STR00009##

[0187] 5.0 g of (3-(2-hydroxypropoxy)propyl)methylsiloxane-co-polydimethylsiloxane (from example 2 Mn: 3596 g/mol) were charged together with 0.015 g of the DMC catalyst (500 ppm based on the amount of the copolymer) and 20.0 g heptane in a 100 mL-stirring Autoclave. The reaction mixture was stirred at room temperature with constant stirring at 350 rpm for several minutes under vacuum (0.001 bar) and argon atmosphere (1 bar). Then the reaction temperature was increased at 110° C. After reaching this temperature, 7.0 mL of propylene oxide (PO) were added to the reaction mixture and stirred constantly at 350 rpm. After filtration the solvent and traces of unreacted monomer were removed under vacuum (0.001 bar) for three hours. The yield of the product was found to be 90%.

Example 4

[0188] F1 to F10 were prepared by mixing the raw materials listed in Table 1. In which the alkoxy base formulation consist of a mixture of 70 wt % α,ω-dimethoxyvinyl-terminated polydimethylsiloxane with an viscosity of 80000 cST (see exact procedure U.S. Pat. No. 5,663,269), 20 wt % polydimethylsiloxane with viscosity of 1000 cST, 9.8 wt % hydrophobic fumed silica and 0.2 wt % tetra-n-butyl titanate. F2 to F8 are according to the present invention with different amounts of polysiloxane polyalkyleneglycol brush copolymer prepared in Example 3. Instead of the polysiloxane polyalkyleneglycol brush copolymer, F9 and F10 contain linear PPG with two terminated OH-groups (Acclaim 8200) and branched PPG with three terminated OH-groups (Acclaim 6300), respectively.

TABLE-US-00001 TABLE 1 Formulations F1 F2 F3 F4 F5 F6 F7 F8 F9 F10 Alkoxy base formulation 100 99 90 80 70 60 50 40 90 90 [wt %] polysiloxane —  1 10 20 30 40 50 60 — — polyalkyleneglycol brush copolymer [wt %] Acclaim 8200 [wt %] — — — — — — — — 10 — Acclaim 6300 [wt %] — — — — — — — — — 10

[0189] Measurement of skin formation time: The determination of the skin formation time was carried out under standard climate conditions (23+/−2° C., relative humidity 50+/−5%). The temperature of the sealant must be 23+/−2° C., with the sealant stored for at least 24 h beforehand in the laboratory. The sealant was applied to a sheet of paper and spread out with a putty knife to form a skin (thickness approximately 2 mm, width approximately 7 cm). The stopwatch was started immediately. At intervals, the surface was touched lightly with the fingertip and the finger was pulled away, with sufficient pressure on the surface that an impression remains on the surface when the skin formation time was reached. The skin formation time was reached when sealing compound no longer adheres to the fingertip.

[0190] Measurement of ShoreA hardness: The procedure was carried out in accordance with ISO 868.

[0191] Measurement of contact angles: The contact angle measuring instrument OCA 40 Micro from the Company DataPhysics the Chair of Fluid Technology and microfluidics was used for the automatic measurement and evaluation of static and dynamic contact angles according to the generalized length—height method for drop-on-fiber arrangement, the static and dynamic contact angle of microscopic objects by the sessile drop method and the automatic determination of the surface free energy of solids and their components. One distilled water drop with a defined volume was dropped on the surface. The contact angle was measured at the beginning and after 30, 60 and 90 seconds.

[0192] Anti-Adhesion Assay: This test is to determine the adhesive properties of a sealant surface towards fungal cells. The method can be used with either yeast cells or mold spores. After a sedimentation and adhesion phase of 60 min, the surfaces are washed, and the remaining cells are washed of using a detergent solution. Afterwards the cell count of that solution is determined by means of plating serial dilutions.

[0193] Preparation of cell suspension: Yeast cells were washed of a well grown plate using an inoculation loop and buffer (0.2% Tween80; 0.9% NaCl). The suspension was filtered through sterile glass wool to remove hyphal fragments. Cells were washed by means of centrifugation and resuspension in autoclaved tap water. This procedure was repeated once. The germ count was adjusted to ˜1.0E+04 by measuring optical density at 600 nm or by employing a hemocytometer or similar methods.

[0194] Test procedure: For each sample six specimen were cut to fit in standard six-well plates (20×20 mm). The wells were filled with cell suspension ensuring that the specimens were completely overlaid. Wells were incubated at RT for 60 min to led cells sediment and adhere to the surface. Afterwards, each specimen was taken out with forceps. Washing took place by slowly dipping the specimen into five consecutive 11-beakers filled with water. Cell recovery was achieved by placing the specimen into a tube with glass beads and 5 ml buffer (0.3% Tween80; 0.9% NaCl; 0.1% Trypton). Tubes were shaken on rotary shaker for 5 min at 200 rpm. A germ count determination from each solution was performed using serial dilutions and an appropriate agar medium (e.g., wort agar). Mean and standard deviation was calculated from each set of six specimen. The mean germ count of each sample was compared to an appropriate control sample.

[0195] The results of the contact angle measurements are shown in Table 2. F1 showed no change in contact angle during time, while F2 to F8 showed a strong spreading effect (decrease of contact angle) of the water droplet during time. In some cases, the change of contact angle after 90 seconds can be more than 20 degrees. This invention discloses polymers with both a special branched microstructure, as well as the combination of different chemical groups which results in an increase of the material's surface energy. Hence, water droplets tend to spread to a higher extend in the formulations containing the brush copolymers according to the present invention, resulting in faster water evaporation and ultimately in a lower surface moisture. F9 and F10 showed a just slight droplet spreading during time.

TABLE-US-00002 TABLE 2 Skin formation ShoreA Contact Angle (°) time (min) 7d t(0), t(30), t(60), t(90) Fl 90 19.0 103.9, 106.4, 104.8, 104.6 F2 45 18.3 106.1, 105.3, 102.0, 99.9 F3 40 21.3 95.9, 91.9, 86.1, 82.0 F4 55 24.3 95.4, 89.9, 85.8, 82.5 F5 50 21.7 110.7, 99.0, 92.3, 89.5 F6 60 17.0 93.0, 88.1, 81.4, 78.5 F7 70 17.7 96.2, 86.6, 81.3, 79.0 F8 40 19.7 97.5, 74.1, 71.4, 69.9 F9 70 19.7 86.2, 84.1, 83.2, 83.1 Fl 0 80 18.0 95.2, 93.6, 92.7, 92.3
Table 3 shows the results for the anti-adhesion assay against black yeasts of F2 to F8 compared to F1 as reference. A great improvement of anti-adhesion properties with F2 to F8 was achieved.

TABLE-US-00003 TABLE 3 F1 F2 F3 F4 F5 F6 F7 F8 Germination number 100 31 24 35 43 49 36 55 compared to F1 (%)