Nanostructured Composite Materials with Self-Healing Properties
20210071001 · 2021-03-11
Inventors
- Carsten Becker-Willinger (Saarbrücken, DE)
- Budiman Ali (Saarbrücken, DE)
- Jessica Brunke (St. Gallen, CH)
- Gerhard Wenz (St. Ingbert, DE)
- Devid Hero (Losheim am See, DE)
Cpc classification
C08B37/0015
CHEMISTRY; METALLURGY
International classification
Abstract
A self-healing composite material includes at least one cross-linked polyrotaxane and at least one organically modified inorganic hybrid material which comprises functional groups (B) or at least one type of surface-modified inorganic particles which have functional groups (B) on their surface. The polyrotaxane is a cross-linked polyrotaxane and at least two of the threaded ring-shaped molecules are cross-linked by linking of the functional groups (A) and (B).
Claims
1. A composition for a self-healing composite material, comprising: a) at least one polyrotaxane comprising a copolymer and ring-shaped molecules threaded thereon, with at least one ring-shaped molecule having at least one functional group (A); b) at least one organically modified inorganic hybrid material which comprises functional groups (B), or at least one kind of surface-modified inorganic particles which on their surface have functional groups (B); where at least two of the threaded ring-shaped molecules can be crosslinked by linking of the functional groups (A) and (B).
2. The composition as claimed in claim 1, wherein the ring-shaped molecule is cyclodextrin or a cyclodextrin derivative.
3. The composition as claimed in claim 1, wherein the organically modified inorganic hybrid material comprises a polyorganosiloxane.
4. The composition as claimed in claim 1, wherein the composition comprises a crosslinker which comprises at least two functional groups and is suitable for entering into a bond both with the functional groups (A) and with the functional groups (B) and so for crosslinking them with one another and to one another.
5. The composition as claimed in claim 1, wherein the inorganic particles are ceramic particles.
6. The composition as claimed in claim 1, wherein the functional groups (A) are hydroxyl groups, thiol groups, carboxylic acid groups, anhydride groups, isocyanate groups, amino groups, monoalkylamino groups, isocyano groups, acrylate groups, methacrylate groups, aldehyde groups, or precursors thereof.
7. The composition as claimed in claim 1, wherein the functional groups (B) are hydroxyl groups, thiol groups, carboxylic acid groups, anhydride groups, isocyanate groups, amino groups, monoalkylamino groups, isocyano groups, acrylate groups, methacrylate groups, aldehyde groups, or precursors thereof.
8. A method for producing the composite material, wherein a composition as claimed in claim 1 is provided and cured.
9. A composite material obtained by curing a composition as claimed in claim 1.
10. A self-healing surface comprising a composite material as claimed in claim 9.
11. A shaped article comprising a composite material as claimed in claim 9.
Description
[0136] The working examples are represented schematically in the figures. Identical reference numerals in the individual figures denote identical or functionally identical elements or elements which correspond to one another in terms of their functions. The figures specifically show the following:
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WORKING EXAMPLES
[0156] Table 9 reports the fraction of component b) as a fraction of the solids content of the composition. This corresponds to the amount in the cured composition. For the designation of the samples and in the figures, the target solids content of component b) has been used.
[0157] The sample designations with PR- refer to coatings, those without S- to the associated paints In the figures PR-S- refer to the cured coatings, the designations PR- without S- to the associated paints.
Example 1: Preparation of a Binary Base Polyrotaxane
[0158] 94.43 g of a RAMEB solution (RAMEB: partly methylated -cyclodextrin, Wacker Chemie) in water (50 wt %, 36 mmol) are admixed with 1.35 ml (1.12 g, 10.8 mmol) of styrene (distilled) and 5 ml of methanol (synthetic grade). Then nitrogen is introduced over 1 h. 0.140 g, 0.43 mmol of radical initiator VA044 (2,2-azobis[2-imidazolin-2-yl)propane) is dissolved with 1 ml of distilled water and likewise degassed for 5 min with nitrogen. After 1 h the system is closed. The reaction mixture is admixed with 8.2 ml (4.9 g, 72 mmol) of 2,3-dimethyl-1,3-butadiene, 0.042 ml of carbon tetrachloride chain transfer agent (0.1 mol % on the polymer chain, degassed for 5 min) and the initiator VA044. Subsequently the temperature was adjusted to 38 C. and the reaction mixture was stirred further for 48 h.
[0159] After the end of the reaction, the polyrotaxane-water mixture is added to cold water containing 10 vol % EtOH and flushed with nitrogen for 20 min. After the filtration, the procedure is repeated twice more. The precipitated polyrotaxane is subsequently dried for 3 d in a vacuum drying cabinet at 80 C. and dissolved in chloroform; following concentration of the chloroform, THF was added and the product was subsequently dried under reduced pressure. Analysis by gel permeation chromatography gives an average molecular weight of M=80 000 g/mol.
Example 2: Preparation of a Ternary Base Polyrotaxane (PR-bru008a*/PR-bru008b*)
[0160] 94.43 g of a RAMEB solution (RAMEB: partly methylated -cyclodextrin, Wacker Chemie) in water (50 wt %, 36 mmol) are admixed with 0.34 ml (0.375 g, 3.6 mmol) of styrene (distilled) and 5 ml of methanol (synthetic grade). Then nitrogen is introduced over 1 h. 0.140 g, 0.43 mmol of radical initiator VA044 (2,2-azobis[2-imidazolin-2-yl)propane) is dissolved with 1 ml of distilled water and likewise degassed for 5 min with nitrogen. After 1 h the system is closed. The reaction mixture is admixed with 8.2 ml (4.9 g, 72 mmol) of 2,3-dimethyl-1,3-butadiene, 6.52 ml (6.20 g, 72 mmol) of methyl acrylate, 0.036 ml of dodecanethiol chain transfer agent (0.1 mol % on the polymer chain, degassed for 5 min) and the initiator VA044. Subsequently the temperature was adjusted to 38 C. and the reaction mixture was stirred further for 48 h. After the end of the reaction, the polyrotaxane-water mixture is added to cold water containing 10 vol % EtOH and flushed with nitrogen for 20 min. After the filtration, the procedure is repeated twice more. The precipitated polyrotaxane is subsequently dried for 3 d in a vacuum drying cabinet at 80 C. and dissolved in chloroform; following concentration of the chloroform, THF was added and the product was subsequently dried under reduced pressure. Analysis by gel permeation chromatography gives an average molecular weight of M=26 000 g/mol (mole fraction 0.012 styrene, 0.004 cyclodextrin, 0.514 isoprene, 0.469 methacrylate).
[0161] Base polyrotaxane PR-bru008*: analogous to PR-bru008a*/PR-bru008b* but with 0.012 ml of dodecanethiol chain transfer agent (0.033 mol % on the polymer chain). Analysis by gel permeation chromatography gives an average molecular weight of M=57 000 g/mol.
[0162] The molar mass and dispersities of the polymers were measured by gel permeation chromatography (GPC) at room temperature. Separation took place with two columns from PSS (Polymer Standards Service, Mainz, Germany (PSS)) SDV 10.sup.3 and 10.sup.5 . The recording was made using a refractive index detector (Shodex RI-101). The mobile phase was tetrahydrofuran (THF) and the flow rate was kept at 1 ml/min with a Viscotek VE1121 GPC pump. The GPC calibration curve was determined using a number of polystyrene standards (from 1 090 000 to 682 g/mol) from PSS.
[0163] The threading rates determined for the samples obtained were as follows:
[0164] PR_bru008*: 1.57%
[0165] PR_bru008a*: 3.42%
[0166] PR_bru008b*: 3.73%
Example 3: Preparation of the Epoxysilane-Modified SiO.SUB.2 .Particles (SiO.SUB.2./GPTES)
[0167] 2.5 ml (3.085 g SiO.sub.2) of MIBK-ST (Nissan, Organosilicasol) were admixed with 1.61 ml of GPTES and stirred at 40 C. for 4 d. The dispersion obtained was used, without further workup, for producing the composites. The solids content of the dispersion is 33.5 wt %. The SiO.sub.2 particles used have a size distribution of d.sub.90<15 nm. The majority of the particles have a diameter of 10-15 nm.
Example 4: Preparation of the Mercaptosilane Hydrolyzate (MPS-Hydrolyzate)
[0168] 5.8911 g of 3-mercaptopropyltrimethoxysilane (MPS) are admixed with 0.3375 g of distilled water. The initially two-phase emulsion was stirred under inert gas at 60 C. for 23 h and became a transparent mixture. The solids content of the resulting mixture, after removal of the solvent at 100 C. in a vacuum drying cabinet, was determined gravimetrically as being 25 wt %.
Example 5: Preparation of the Mercaptosilane-Modified CeO.SUB.2 .Particles (CeO.SUB.2./MPS)
[0169] 0.3398 g of a 20 wt % CeO.sub.2 dispersion in water (Sigma-Aldrich) were admixed with 1.974 g of 3-mercaptopropyltrimethoxysilane (MPS). The initially two-phase emulsion, after stirring under inert gas at 60 C. for 17 h, became a transparent dispersion. The solids content of the resulting dispersion, after removal of the solvent at 100 C. in a vacuum drying cabinet, was determined gravimetrically as being 81.3 wt %. The CeO.sub.2 particles used have a particle size of 30-50 nm.
[0170] Coating Materials
Example 6: Unfilled, Crosslinked Polymer: PR-S-171214-Bru-1 (PR-bru008*; Coating)/PR-S-171204-bru-1 (PR-bru008a*)/PR-S-180111-bru-1 (PR-bru008b*)/PR-171115-ali-1 (PR-bru008*; Film)
[0171] 1.3 g of polyrotaxane paint base (30 wt % PR-bru008*/PR-bru008a*/PR-bru008b* in MPA) are diluted with 0.613 g of MPA (1-methoxy-2-propyl acetate). After 5 min of stirring, 0.075 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA) are added and mixed in for a further 5 min. The resulting mixture has a solids content of 20 wt % and a total mass of 1.99 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 7: PR-S-171121-bru-1 PR with 1% SiO.SUB.2./GPTES
[0172] 5 g of polyrotaxane paint base (30 wt % PR-bru008* in MPA) are diluted with 2.382 g of MPA. After 5 min of stirring, 0.051 g of functionalized SiO.sub.2 particles from example 3 is added and the mixture is stirred for 30 min. Following addition of 0.2871 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 7.72 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 8: PR-S-171121-bru-2 5% SiO.SUB.2./GPTES
[0173] 5 g of polyrotaxane paint base (30 wt % PR-bru008* in MPA) are diluted with 2.484 g of MPA. After 5 min of stirring, 0.255 g of functionalized SiO.sub.2 particles from example 3 is added and the mixture is stirred for 30 min. Following addition of 0.2871 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 8.03 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 9: PR-S-171127-bru-1 10% SiO.SUB.2./GPTES
[0174] 5 g of polyrotaxane paint base (30 wt % PR-bru008* in MPA) are diluted with 2.611 g of MPA. After 5 min of stirring, 0.510 g of functionalized SiO.sub.2 particles from example 3 is added and the mixture is stirred for 30 min. Following addition of 0.2871 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 8.41 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 10: PR-S-171127-bru-2 20% SiO.SUB.2./GPTES
[0175] 5 g of polyrotaxane paint base (30 wt % PR-bru008* in MPA) are diluted with 2.866 g of MPA. After 5 min of stirring, 1.019 g of functionalized SiO.sub.2 particles from example 3 are added and the mixture is stirred for 30 min. Following addition of 0.2871 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 9.17 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 11: PR-S-171127-bru-3 30% SiO.SUB.2./GPTES
[0176] 5 g of polyrotaxane paint base (30 wt % PR-bru008* in MPA) are diluted with 3.121 g of MPA. After 5 min of stirring, 1.529 g of functionalized SiO.sub.2 particles from example 3 are added and the mixture is stirred for 30 min. Following addition of 0.2871 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 9.94 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
[0177]
[0178]
Example 12: PR-S-171204-bru-2 1% MPS Hydrolyzate
[0179] 5 g of polyrotaxane paint base (30 wt % PR-bru008a* in MPA) are diluted with 2.282 g of MPA. After 5 min of stirring, 0.062 g of MPS hydrolyzate from example 4 is added and the mixture is stirred for 30 min. Following addition of 0.467 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 7.81 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 13: PR-S-171204-bru-3 5% MPS Hydrolyzate
[0180] 5 g of polyrotaxane paint base (30 wt % PR-bru008a* in MPA) are diluted with 2.344 g of MPA. After 5 min of stirring, 0.309 g of MPS hydrolyzate from example 4 is added and the mixture is stirred for 30 min. Following addition of 0.467 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 8.12 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 14: PR-S-171213-bru-1 10% MPS Hydrolyzate
[0181] 5 g of polyrotaxane paint base (30 wt % PR-bru008a* in MPA) are diluted with 2.421 g of MPA. After 5 min of stirring, 0.619 g of MPS hydrolyzate from example 4 is added and the mixture is stirred for 30 min. Following addition of 0.467 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 8.51 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 15: PR-S-171213-bru-2 20% MPS Hydrolyzate
[0182] 5 g of polyrotaxane paint base (30 wt % PR-bru008a* in MPA) are diluted with 2.576 g of MPA. After 5 min of stirring, 1.237 g of MPS hydrolyzate from example 4 are added and the mixture is stirred for 30 min. Following addition of 0.467 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 9.28 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 16: PR-S-171213-bru-3 30% MPS Hydrolyzate
[0183] 5 g of polyrotaxane paint base (30 wt % PR-bru008a* in MPA) are diluted with 2.731 g of MPA. After 5 min of stirring, 1.856 g of MPS hydrolyzate from example 4 are added and the mixture is stirred for 30 min. Following addition of 0.467 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 10.05 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
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[0185]
Example 17: PR-S-180111-bru-2 1% CeO.SUB.2./MPS
[0186] 5.003 g of polyrotaxane paint base (30 wt % PR-bru008b* in MPA) are diluted with 2.269 g of MPA. After 5 min of stirring, 0.0196 g of functionalized CeO.sub.2 particles from example 5 is added and the mixture is stirred for 30 min. Following addition of 0.574 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 7.87 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 18: PR-S-180111-bru-3 5% CeO.SUB.2./MPS
[0187] 5.000 g of polyrotaxane paint base (30 wt % PR-bru008b* in MPA) are diluted with 2.504 g of MPA. After 5 min of stirring, 0.0998 g of functionalized CeO.sub.2 particles from example 5 is added and the mixture is stirred for 30 min. Following addition of 0.575 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 8.18 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 19: PR-S-180118-bru-1 10% CeO.SUB.2./MPS
[0188] 4.808 g of polyrotaxane paint base (30 wt % PR-bru008b* in MPA) are diluted with 2.678 g of MPA. After 5 min of stirring, 0.182 g of functionalized CeO.sub.2 particles from example 5 is added and the mixture is stirred for 30 min. Following addition of 0.549 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 8.22 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 20: PR-S-180118-bru-2 20% CeO.SUB.2./MPS
[0189] 4.397 g of polyrotaxane paint base (30 wt % PR-bru008b* in MPA) are diluted with 2.982 g of MPA. After 5 min of stirring, 0.338 g of functionalized CeO.sub.2 particles from example 5 is added and the mixture is stirred for 30 min. Following addition of 0.505 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 8.22 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 21: PR-S-180118-bru-3 30% CeO.SUB.2./MPS
[0190] 4.004 g of polyrotaxane paint base (30 wt % PR-bru008b* in MPA) are diluted with 3.179 g of MPA. After 5 min of stirring, 0.461 g of functionalized CeO.sub.2 particles from example 5 is added and the mixture is stirred for 30 min. Following addition of 0.458 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 8.10 g. 0.8 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
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Example 22: PR-S-180102-bru-1 with Hydrophobizing on the CD
[0193] 1.1 g of polyrotaxane paint base (30 wt % PR_bru008* in MPA) are admixed with 0.024 g of hexyl isocyanate stock solution (10 wt % in MPA), stirred under nitrogen at 60 C. for 22 h, and then diluted with 0.52 g of MPA. After 5 min of stirring, 0.032 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA) is added and mixed for a further 5 min. The resulting mixture has a solids content of 20 wt % and a total mass of 1.67 g. 0.7 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 23: PR-S-180106-bru-1 with Hydrophobizing on the CD+10% SiO.SUB.2./GPTES
[0194] 1.01 g of polyrotaxane paint base (30 wt % PR-bru008* in MPA) are admixed with 0.0026 g of hexyl isocyanate stock solution (10 wt % in MPA), stirred under nitrogen at 60 C. for 22 h, and then diluted with 0.52 g of MPA. After 5 min of stirring, 0.104 g of functionalized SiO.sub.2 particles from example 3 are added and the mixture is stirred for 30 min. After addition of 0.029 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), the resulting mixture has a solids content of 20 wt % and a total mass of 1.69 g. 0.7 ml of the paint in each case is subsequently applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and the paint is cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
[0195] Shaped Articles
Example 24: Production of Shaped Articles of PR-171127-/PR-171121x % SiO.SUB.2./GPTES
[0196] Shaped articles with a size of 25 mm25 mm1 mm (for DE spectroscopy) and 20 mm10 mm1 mm (for DMTA measurements;
Example 25: Production of Shaped Articles of PR-171204-/PR-171213x % MPS Hydrolyzate
[0197] Shaped articles with a size of 25 mm25 mm1 mm (for DE spectroscopy) and 20 mm10 mm1 mm (for DMTA measurements;
Example 26: Production of Shaped Articles of PR-180111-/PR-180118x % CeO.SUB.2./MPS
[0198] Shaped articles with a size of 25 mm25 mm1 mm (for DE spectroscopy) and 20 mm10 mm1 mm (for DMTA measurements) are produced in PTFE casting molds. The casting molds are each cautiously filled, without air bubbles, with the mixtures from examples 17-21, and the solvent is removed in a vacuum drying cabinet at 60 C. for 1 h under 300 mbar, without starting the crosslinking reaction. This procedure is repeated a total of ten times, until the solvent-free shaped article has reached a thickness of around 1 mm. Thereafter the entire layer construction is dried in a vacuum drying cabinet at 60 C. for 12 h at 100 mbar to remove residual solvent. The final curing of the mixtures in the casting mold takes place subsequently over 30 h at 120 C. The resulting shaped article is transparent and slightly yellowish.
Example 27: PR-S-180124-bru-1 with Hydrophobizing on the CD, Binary System
[0199] 0.104 g of PR_bru010* was dissolved in 0.412 g of MPA and 0.821 g of chlorobenzene and the solution was admixed with 0.308 g of hexyl isocyanate stock solution (10 wt % in MPA) and stirred under nitrogen at 120 C. for 22 h. The solvents were removed under a high vacuum. The residue was dissolved in 0.329 g of MPA and the solution was stirred for 5 min. Following addition of 0.142 g of Desmodur N 3900 stock solution crosslinker (10 wt % Desmodur N 3900 in MPA), mixing took place again for 5 min. The resulting mixture has a solids content of 20 wt % and a total mass of 0.57 g. Subsequently 0.25 ml of the paint in each case is applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and cured in an oven at 120 C. for 3 h. A well-adhering, transparent coating is formed.
Example 28: PR-S-180206_bru-1 with Hydrophobizing on the CD with Methyl Acrylate, Ternary System
[0200] 0.1 g of PR_bru008b* was dissolved in 2.45 g of pyridine (abs.), admixed with 0.0032 g of methacrylic anhydride, and stirred under inert gas at 60 C. for 24 h. The solvents were removed via distillation. The residue was dissolved with 0.394 g of MPA. After 5 min of stirring, 0.177 g of camphorquinone and 0.206 g of ethyl 4-dimethylaminobenzoate for crosslinking are added (50 mol % relative to the methacrylic acid used), and mixing continues for 5 min. The resulting mixture has a solids content of 20 wt % and a total mass of 0.51 g. Subsequently 0.20 ml of the paint in each case is applied by spin coating to a black-painted stainless steel panel or to a stainless steel substrate cleaned with ethanol, and cured for 2 min with a mercury vapor lamp. A well-adhering, transparent coating is formed.
[0201] Time-Temperature Dependence of the Self-Healing
[0202] For this, at different temperatures, the time (t) up to the disappearance of scratches (scratch depth around 0.8 m-1.2 m (after scratch test with 50 g) was measured.
[0203] Table 1 shows the results for PR modified with MPS hydrolyzate (measurement on black paint).
[0204] Table 2 shows the results for PR modified with CeO.sub.2/MPS hydrolyzate (measurement on black paint).
[0205] Table 3 shows the results for PR modified with SiO.sub.2/GPTES hydrolyzate (measurement on black paint).
[0206] Table 4 shows the results for the hydrophobized systems.
[0207] It emerges that the addition of component b) does not restrict the capacity of the material to self-heal, and in part in fact improves it. This is also apparent from the values measured in
[0208] Table 5 shows the results of the measurement of the contact angle (measurement on stainless steel) against H.sub.2O for PR modified with SiO.sub.2/GPTES with and without hydrophobizing on the polymer matrix.
[0209] The microhardness of the samples was measured at 20 C. (penetration depth: 1 m, HM: Martens hardness, E.sub.red: reduced elastic modulus, HU.sub.pl: plastic hardness (=resistance to plastic deformation)). Tables 6, 7, and 8 show the results of a PR modified with MPS hydrolyzate (measurement on stainless steel, table 6,
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[0211]
[0212]
TABLE-US-00001 TABLE 1 t/s t/s t/s System MPS/wt % at 80 C. at 90 C. at 100 C. PR-S-171204-bru-1 0 480 160 PR-S-171204-bru-2 1 1200 480 PR-S-171204-bru-3 5 180 60 PR-S-171213-bru-1 10 120 90 PR-S-171213-bru-2 20 360 PR-S-171213-bru-3 30 480
TABLE-US-00002 TABLE 2 t/s t/s t/s System CeO.sub.2 /wt % at 80 C. at 90 C. at 100 C. PR-S-180111-bru-1 0 840 100 PR-S-180111-bru-2 1 420 240 PR-S-180111-bru-3 5 300 60 PR-S-180118-bru-1 10 480 150 PR-S-180118-bru-2 20 720 180 PR-S-180118-bru-3 30 >1800 180
TABLE-US-00003 TABLE 3 t/s t/s t/s System SiO.sub.2/wt % at 80 C. at 90 C. at 100 C. PR-S-171214-bru-1 0 840 70 40 PR-S-171121-bru-1 1 840 80 70 PR-S-171121-bru-2 5 1200 180 100 PR-S-171127-bru-1 10 720 160 PR-S-171127-bru-2 20 300 PR-S-171127-bru-3 30 >1800
TABLE-US-00004 TABLE 4 t/s t/s t/s System SiO.sub.2/wt % at 80 C. at 90 C. at 100 C. PR-S-171214-bru-1 0 840 70 40 PR-S-171127-bru-1 10 720 160 PR-S-180102-bru-1 0 Hex PR-S-180106-bru-1 10 300 240 Hex
TABLE-US-00005 TABLE 5 System Hydrophobizing SiO.sub.2/wt % CA (H.sub.2O)/ PR-S-171214-bru-1 0 61 3 PR-S-180102-bru-1 Hexyl isocyanate 0 86 1 PR-S-180106-bru-1 Hexyl isocyanate 10 94 2
TABLE-US-00006 TABLE 6 System MPS/wt % HM/MPa E.sub.red/MPa HU.sub.pl/MPa PR-S-171204-bru-1 0 239 22 .sup.8340 2300 308 15 PR-S-171204-bru-2 1 243 4 8180 210 314 5 PR-S-171204-bru-3 5 237 21 .sup.8700 1870 297 14 PR-S-171213-bru-1 10 169 9 9200 410 178 15 PR-S-171213-bru-2 20 96 3 18 800 3500 86 4 PR-S-171213-bru-3 30 107 5 11 850 1300 99 5
TABLE-US-00007 TABLE 7 CeO.sub.2/ System wt % HM/MPa E.sub.red/MPa HU.sub.pl/MPa PR-S-180111-bru-1 0 242 26 9980 2550 285 18 PR-S-180111-bru-2 1 266 22 9930 2120 329 15 PR-S-180111-bru-3 5 234 15 8490 1030 292 12 PR-S-180118-bru-1 10 195 10 9010 1010 217 10 PR-S-180118-bru-2 20 74 27 n.d. n.d. PR-S-180118-bru-3 30 75 9 18 500 3160.sup. 68 8
TABLE-US-00008 TABLE 8 System SiO.sub.2/wt % HM/MPa E.sub.red/MPa HU.sub.pl/MPa PR-S-171214-bru-1 0 154 4 5750 153 178 6 PR-S-171121-bru-1 1 201 10 6500 370 260 18 PR-S-171121-bru-2 5 246 42 .sup.9910 4250 304 47 PR-S-171127-bru-1 10 287 57 15 630 7280 316 39 PR-S-171127-bru-2 20 258 34 10 540 2650 306 26 PR-S-171127-bru-3 30 230 27 .sup.9166 2890 273 19
TABLE-US-00009 TABLE 9 Target solids content Solids content Example of component b) of component b) No. Component b) [wt %] [wt %] 7 SiO.sub.2/GPTES 1 1.11 8 SiO.sub.2/GPTES 5 5.29 9 SiO.sub.2/GPTES 10 10.05 10 SiO.sub.2/GPTES 20 18.25 11 SiO.sub.2/GPTES 30 25.1 12 MPS hydrolyzate 1 0.99 13 MPS hydrolyzate 5 4.76 14 MPS hydrolyzate 10 9.1 15 MPS hydrolyzate 20 16.66 16 MPS hydrolyzate 30 23.08 17 CeO.sub.2/MPS 1 1.01 18 CeO.sub.2/MPS 5 4.95 19 CeO.sub.2/MPS 10 8.99 20 CeO.sub.2/MPS 20 16.71 21 CeO.sub.2/MPS 30 23.11
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