POLYMER DISPERSIONS CONTAINING ACYLMORPHOLINES

Abstract

The present invention relates to N-acylmorpholines as solvents for use in processes for preparing polymer dispersions.

Claims

1. An aqueous polymer dispersion, comprising at least one N-acylmorpholine of formula (I) ##STR00002## where R.sub.1 is H or an alkyl radical having 1 to 18C atoms, and R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently of one another are a hydrogen atom or a (cyclo)alkyl radical having 1 to 18C atoms.

2. The polymer dispersion according to claim 1, comprising 0.01 wt % to 30 wt % of the at least one N-acylmorpholine of formula (I).

3. The polymer dispersion according to claim 1, wherein R.sub.1 is selected from the group consisting of H, methyl, and ethyl.

4. The polymer dispersion according to claim 1, wherein R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, and cyclohexyl.

5. The polymer dispersion according to claim 1, wherein the N-acylmorpholine is at least one morpholine selected from the group consisting of N-formylmorpholine, N-acetylmorpholine, and N-propionylmorpholine.

6. The polymer dispersion according to claim 1, which is a polyurethane dispersion.

7. A process for preparing the polymer dispersion according to claim 6, the process comprising: (A) preparing a polyurethane in the presence of the N-acylmorpholine of formula (I); and (B) subsequently dispersing the polyurethane in water.

8. The process according to claim 7, wherein the preparing (A) is carried out by reacting a) at least one polyfunctional isocyanate having 4 to 30C atoms, b) diols which comprises b1) 10 to 100 mol %, based on a total amount of the diols (b), of a diol having a molecular weight of 500 to 5000, and b2) 0 to 90 mol %, based on the total amount of the diols (b), of a diol having a molecular weight of 60 to 500 g/mol, c) optionally at least one polyfunctional compound, which is different from the diols (b) and has reactive groups selected from the group consisting of an alcoholic hydroxyl group, a primary amino group, and a secondary amino group, and d) at least one monomer different from (a), (b), and (c) and comprising at least one isocyanate group or at least one group reactive toward an isocyanate group, and at least one hydrophilic group or potentially hydrophilic group, to give the polyurethane, and the process optionally further comprises adding polyamines after or during the dispersing (B).

9. The process according to claim 7, wherein R.sub.1 is selected from the group consisting of H, methyl, ethyl.

10. The process according to claim 7, wherein R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, and cyclohexyl.

11. The process according to claim 7, wherein the N-acylmorpholine is at least one morpholine selected from the group consisting of N-formylmorpholine, N-acetylmorpholine, and N-propionylmorpholine.

12. A method for coating and adhesive bonding wood, wood veneer, paper, paperboard, cardboard, textile, leather, synthetic leather, nonwoven, plastics surfaces, glass, ceramic, mineral construction materials, metals, or coated metals, the method comprising applying the polymer dispersion according to claim 1 to the wood, wood veneer, paper, paperboard, cardboard, textile, leather, synthetic leather, nonwoven, plastics surfaces, glass, ceramic, mineral construction materials, metals, or coated metals.

13. A method for preparing a polyurethane, the method comprising: preparing the polyurethane from a substituted N-acylmorpholines of formula (I) ##STR00003## where R.sup.1 is H or an alkyl radical having 1 to 18C atoms, and R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently of one another are a hydrogen atom or a (cyclo)alkyl radical having 1 to 18C atoms.

14. A method for coating a surface, the method comprising applying the polymer dispersion according to claim 1 to the surface.

15. A coating composition, comprising the polymer dispersion according to claim 1.

16. A method for coating and adhesive bonding wood, wood veneer, paper, paperboard, cardboard, textile, leather, synthetic leather, nonwoven, plastics surfaces, glass, ceramic, mineral construction materials, metals, or coated metals, the method comprising applying a polyurethane dispersion obtained by the process according to claim 7 to the wood, wood veneer, paper, paperboard, cardboard, textile, leather, synthetic leather, nonwoven, plastics surfaces, glass, ceramic, mineral construction materials, metals, or coated metals.

Description

EXAMPLES

[0166] I. Preparation of Polyurethane Dispersions

[0167] Abbreviations

[0168] DETA Diethylenetriamine

[0169] DMEA Dimethylethanolamine

[0170] DMPA Dimethylolpropionic acid

[0171] EDA Ethylenediamine

[0172] IPDA Isophoronediamine

[0173] IPDI Isophorone diisocyanate

[0174] NEP N-Ethylpyrrolidone

[0175] NMP N-Methylpyrrolidone

[0176] PUD Polyurethane dispersion

[0177] TDI Tolylene diisocyanate (80% 2,4- and 20% 2,6-isomer)

[0178] TEA Triethylamine

Example 1

Formylmorpholine as Solvent

[0179] A stirring flask with reflux condenser and thermometer was charged with 400 g (0.20 mol) of a polypropylene oxide with an OH number of 56, 32.2 g (0.24 mol) of DMPA, and 50 g of N-formylmorpholine, and this initial charge was stirred at 65 C. 76.6 g (0.44 mol) of TDI were added and the mixture was stirred at 110 C. for 360 minutes. It was then diluted with 400 g of acetone and the NCO content was found to be 0.01 wt % (calculated: 0.00%). After this, 10.0 g (0.10 mol) of TEA were added. Following dispersion with 800 g of water, the acetone was removed by distillation under reduced pressure.

[0180] This gave a finely divided PUD with a 44.8% solids content and a viscosity of 23 mPas at 23 C. and a shear rate of 250/s.

Example 2

Acetylmorpholine as Solvent

[0181] A stirring flask with reflux condenser and thermometer was charged with 400 g (0.20 mol) of a polypropylene oxide with an OH number of 56, 32.2 g (0.24 mol) of DMPA, and 50 g of acetylmorpholine, and this initial charge was stirred at 65 C. 76.6 g (0.44 mol) of TDI were added and the mixture was stirred at 110 C. for 360 minutes. It was then diluted with 400 g of acetone and the NCO content was found to be 0.03 wt % (calculated: 0.00%). After this, 10.0 g (0.10 mol) of TEA were added. Following dispersion with 800 g of water, the acetone was removed by distillation under reduced pressure.

[0182] This gave a finely divided PUD with a 38.4% solids content and a viscosity of 17 mPas at 23 C. and a shear rate of 250/s.

Comparative Example 3

[0183] Example 1 was repeated, but with 50 g of NMP instead of the N-formylmorpholine. The NCO content was found to be 0.01 wt % (calculated: 0.00%).

[0184] This gave a finely divided PUD with a 44.1% solids content and a viscosity of 99 mPas at 23 C. and a shear rate of 250/s.

Comparative Example 4

[0185] Example 1 was repeated, but with 50 g of NEP instead of the N-formylmorpholine. The NCO content was found to be 0.02 wt % (calculated: 0.00%).

[0186] This gave a finely divided PUD with a 40.1% solids content and a viscosity of 285 mPas at 23 C. and a shear rate of 250/s.

TABLE-US-00001 TABLE 1 Properties of polymer dispersions in examples 1 to 4. Solid content Viscosity Example Solvent (%) (mPas) 1 Formylmorpholine 44.8 23 2 Acetylmorpholine 38.4 17 3 NMP 44.1 99 4 NEP 40.1 285

Comparative Example 5

NMP

[0187] A stirring flask with reflux condenser and thermometer was charged with 400 g (0.20 mol) of a polyester diol with an OH number of 56 prepared from neopentyl glycol, hexane-1,6-diol and adipic acid, and with 26.09 g (0.19 mol) of DMPA and 150 g of NMP, and this initial charge was stirred at 80 C. for 30 minutes. 175.5 g (0.79 mol) of IPDI were added and the mixture was stirred at 95 C. After four hours, an NCO content of 4.44% was reached (calculated: 4.41%). Following the addition of 19.71 g (0.19 mol) of TEA, the prepolymer was dispersed in 672 g of water. The dispersion was admixed with a mixture of 66 g of water and 22.53 g of EDA.

Example 6

Formylmorpholine

[0188] The procedure of comparative example 8 was repeated, but replacing the NMP by the same mass of formylmorpholine.

Example 7

Acetylmorpholine

[0189] The procedure of comparative example 8 was repeated, but replacing the NMP by the same mass of acetylmorpholine.

[0190] The dispersions from examples 5, 6 and 7 were poured out into a glass tray and dried at room temperature for 7 days to produce films. The amount of dispersion was chosen so as to give dry films having a thickness of about 1 mm.

[0191] Table 2 summarizes the properties of the dispersions and of the films obtained from them.

[0192] The viscosities were determined with a Paar Physica rotational viscometer in accordance with DIN 53019.

[0193] For determining the LT (light transmittance), each of the polymer dispersions under investigation, in aqueous dilution in a cuvette with a cuvette with an edge length of 2.5 cm, is subjected to measurement with light with a wavelength of 600 nm, and compared with the corresponding transmittance of water under the same measurement conditions. The transmittance of water is stated here as 100%. The more finely divided the dispersion, the higher the LT as measured by the method described above. The LT values were determined for the dispersion in question as a 0.1% strength aqueous solution, using a Hach DR/2010 instrument, at a wavelength of 600 nm.

[0194] The average particle sizes were determined by dynamic light scattering in a Malvern Zetasizer APS.

[0195] The film hardnesses (Shore hardnesses) were determined according to DIN EN ISO 868.

[0196] Tensile Strength and elongation at break were determined according to ISO 37.

TABLE-US-00002 TABLE 2 Properties of the dispersions from examples 5 to 7 and of the films obtained from them. Comparative Example 6 Example 7 example 5 Formylmor- Acetylmor- NMP pholine pholine Solids content (%) 40.4 40.3 40.4 pH 8.95 8.64 8.47 Viscosity (mPas) 102 40 64 LT (%) 98.5 98.6 98.1 Average particle size (nm) 74 71 70 Film properties Shore hardness A 90 88 89 Shore hardness D 41 40 41 Tensile strength (N/mm2) 61 55 66 Elongation at break 711 708 710

[0197] It is clearly seen that the use of acylmorpholines produces dispersions having reduced viscosity and films having identical properties.

[0198] II. Seasoning of Leather

[0199] Products used:

[0200] Lepton Farben N

[0201] Lepton Farben N products are colored, casein-free leather finishers.

[0202] Lepton Filler FCG

[0203] Lepton Filler FCG is a leather finishing filler based on aqueous wax dispersions, matting agent and additives.

[0204] Astacin Finish SUSI TF

[0205] Astacin Finish SUSI TF is a very soft bottoming binder based on an aliphatic polyesterurethane dispersion.

[0206] Astacin Finish PS

[0207] Astacin Finish PS is a soft bottoming binder based on an aliphatic polyetherurethane dispersion.

[0208] Astacin Finish PTM

[0209] Astacin Finish PTM is a hard and matt bottoming binder based on an aliphatic polyetherurethane dispersion and matting agent.

[0210] Corial Binder DN

[0211] Corial Binder DN is a soft bottoming binder with very good low-temperature flexibility, based on an acrylate polymer dispersion.

[0212] Astacin Novomatt GG

[0213] Astacin Novomatt GG is a moderately hard, matt and flexible topcoat binder based on an aliphatic polyesterurethane dispersion and matting agent.

[0214] Astacin Matting HS

[0215] Astacin Matting HS is a hard, matt and flexible topcoat binder based on a polycarbonate dispersion and matting agent.

[0216] Astacin Novomatt GG

[0217] Astacin Novomatt GG is a moderately hard, very matt and flexible topcoat binder based on an aliphatic polyesterurethane dispersion, matting agent and additives.

[0218] Lepton Protector SR

[0219] Lepton Protector SR is an antisoiling auxiliary based on a modified acrylate polymer dispersion and additives.

[0220] Lepton Matting AL

[0221] Lepton Matting AL is a silicate-free, polymeric matting agent.

[0222] Lepton Wax WN

[0223] Lepton Wax WN is a silicone emulsion based on high molecular mass polysiloxanes.

[0224] Lepton Wax DS

[0225] Lepton Wax DS is a silicone emulsion with minimal film-forming, based on high molecular mass polysiloxanes.

[0226] Amollan SW

[0227] Amollan SW is a leveling assistant based on a low-viscosity silicone polyether liquid.

[0228] Astacin Hardener CA

[0229] Astacin Hardener CA is a crosslinker for leather finishing, based on polycarbonate and emulsifiers.

[0230] Astacin Hardener CN

[0231] Astacin Hardener CN is a crosslinker for leather finishing, based on an aliphatic polyisocyanate and organic solvent.

Comparative Example

[0232] 1. First Bottoming:

[0233] A leather suitable for applications in the automotive interior sector was bottomed, using a roll coater, with a liquor containing

[0234] 150 parts Lepton Farben N

[0235] 100 p. Lepton Filler FCG

[0236] 100 p. Astacin Finish SUSI TF

[0237] 150 p. Astacin Finish PS

[0238] 100 p. Astacin Finish PTM

[0239] 100 p. Corial Binder DN

[0240] 65 p. Astacin Novomatt GG

[0241] 5 p. Amollan SW

[0242] 40 p. Astacin Hardener CA.

[0243] The liquor is adjusted by addition of 30 parts of water to a flow viscosity of 40 sec in the 4 mm cup according to DIN EN ISO 2431:2011.

[0244] The wet application weight was 8.00.5 g/ft.sup.2. The leathers were dried at 80 C. for 1.5 minutes in a forced-air drying tunnel.

[0245] 2. Second Bottoming:

[0246] The leather singly bottomed accordingly was bottomed a second time by spray application of a liquor containing

[0247] 150 parts Lepton Farben N

[0248] 100 p. Lepton Filler FCG

[0249] 100 p. Astacin Finish SUSI TF

[0250] 150 p. Astacin Finish PS

[0251] 100 p. Astacin Finish PTM

[0252] 100 p. Corial Binder DN

[0253] 65 p. Astacin Novomatt GG

[0254] 5 p. Amollan SW

[0255] 40 p. Astacin Hardener CA.

[0256] The liquor is adjusted by addition of 130 parts of water to a flow viscosity of 24 sec in the 4 mm cup according to DIN EN ISO 2431:2011.

[0257] The wet application weight was 2.40.2 g/ft.sup.2. The leathers were dried at 80 C. for 1.5 minutes in a forced-air drying tunnel.

[0258] The bottomed leather was stored overnight, embossed at a temperature of 140 C./a pressure of 210 bar/in a residence time of 3 seconds, stored for 3 hours, and milled for 3 hours.

[0259] 3. First Seasoning:

[0260] The doubly bottomed leather was seasoned the first time by means of spray application of a liquor containing

[0261] 150 parts Lepton Farben N

[0262] 60 p. Lepton Filler FCG

[0263] 100 p. Astacin Finish SUSI TF

[0264] 150 p. Astacin Finish PS

[0265] 75 p. Astacin Finish PTM

[0266] 200 p. Astacin Matting HS

[0267] 65 p. Astacin Novomatt GG

[0268] 3 p. Amollan SW

[0269] 60 p. Astacin Hardener CN.

[0270] The liquor is adjusted by addition of 220 parts of water to a flow viscosity of 20 sec in the 4 mm cup according to DIN EN ISO 2431:2011.

[0271] The wet application weight was 2.00.2 g/ft.sup.2.

[0272] The leathers were dried at 80 C. for 1.5 minutes in a forced-air drying tunnel.

[0273] 4. Second Seasoning:

[0274] The singly seasoned leather was seasoned the second time by means of spray application of a liquor containing

[0275] 20 parts Lepton Farben N

[0276] 350 p. Astacin Matting HS

[0277] 150 p. Astacin Novomatt GG

[0278] 75 p. Lepton Protector SR

[0279] 40 p. Lepton Matting AL

[0280] 40 p. Lepton Wax WN

[0281] 40 p. Lepton Wax DS

[0282] 3 p. Amollan SW

[0283] 120 p. Astacin Hardener CN.

[0284] The liquor is adjusted by addition of 330 parts of water to a flow viscosity of 28 sec in the 4 mm cup according to DIN EN ISO 2431:2011.

[0285] The wet application weight was 2.00.2 g/ft.sup.2.

[0286] The leathers were dried at 80 C. for 1.5 minutes in a forced-air drying tunnel.

[0287] The bottomed and seasoned leather was stored overnight.

Inventive Example

[0288] Steps 1. and 2. of the comparative example were repeated.

[0289] In steps 3. and 4., 50 p. N-formylmorpholine in each case were added to the liquor.

[0290] Testing

[0291] After each coating step, the wet adhesion of the finish was tested in accordance with DIN EN ISO 11644.

TABLE-US-00003 Wet adhesion of the finish according to DIN EN ISO 11644/N/cm) 1st 2nd 1st 2nd bottoming bottoming seasoning seasoning Comparative 5.7 4.0 2.0 3.5 example Inventive 5.2 4.7 3.0 8.9 example