Patent ID: 12234311

EXAMPLES

Synthesis of Glycidylamine Monomer

In a 500 mL round bottom flask 85.7 mL (60.0 g, 820 mmol, 1.00 eq.) Diethylamine were solved in a 40 wt % sodium hydroxide solution (49.5 g, 1230 mmol, 1.50 eq. NaOH in 73.8 ml H2O). Under stirring and ice cooling epichlorohydrin (96.5 mL, 114 g, 1230 mmol, 1.50 eq.) was added slowly. After complete addition, the reaction mixture was stirred for additional 24 h while warming up slowly to room temperature. During the reaction, sodium chloride precipitated as a white solid. Water was added to the reaction mixture until the white solid was completely dissolved. The aqueous reaction mixture was extracted three times with diethyl ether and the organic phase was dried with MgSO4. The diethyl ether was removed in vacuum to gain the crude product.

The crude product was purified via fractional distillation in vacuum. In the first fraction, excess epichlorohydrin was collected. In the second fraction diethyl glycidylamine was received with a yield of about 60% (Tb=35-40° C., 12-20 mbar).

The synthesis procedure is identically for other glycidyl amine monomers like pyrrolidine glycidyl amine (PyGA) and dibenzyl glycidyl amine (DBGA).

PyGA: Yield=60% (Tb=45° C., 2 mbar).

Synthesis of Amphiphilic Triblock Copolymers Via Ring-Opening Polymerization Reaction

Synthesis of Diblock Copolymer mPEG-Block-PDEGA-OH

Variant A with Catalyst 18-Crown-6:

In a 500 mL flask equipped with a stirrer and a cooler 37.0 g (18.5 mmol, 1.00 eq.) mPEG were mixed with 0.623 g (5.60 mmol, 0.30 eq.) potassium-tert-butoxide and 1.71 g (6.50 mmol, 0.35 eq.) 18-crown-6. In the next step, 25 mL benzene and 3 mL methanol were added. The mixture was stirred 30 min at 60° C. followed by removal of the solvents and the resulting tert-butanol in vacuum gaining the deprotonated mPEG macro-initiator. The glycidyl amine monomer DEGA was added (8.1 mL, 7.2 g, 56 mmol, 3.0 eq.) into the flask under inert gas atmosphere and the reaction mixture was stirred at 75° C. for 8 hours. The full conversion of the glycidylamine epoxide monomer was verified via1H-NMR spectroscopy and size exclusion chromatography (SEC) measurements. The hydroxyl-functional diblock copolymer was used in the next reaction step without further clean-up procedure.

The synthesis procedure is analogous for other glycidyl amine monomers like PyGA and DBGA.

If so desired, the preparation can be carried out without 18-crown-8 (Variant B).

Synthesis of the Amphiphilic Triblock Copolymer mPEG-Block-PDEGA-Block-PPO

The reaction mixture of the previously described step was cooled down to 40° C. and propylene oxide was added (59.7 mL, 851 mmol, 60 eq.). The reaction mixture was stirred at 40° C. for 24 h to gain the amphiphilic triblock copolymer. The conversion of the propylene oxide was monitored via1H NMR spectroscopy and the final polymer was analyzed via SEC. Residual PO was removed in vacuum.

Quaternization of Tertiary Amine Groups of the Amphiphilic Triblock Copolymer mPEG-Block-P(DEGA)-block-PPO

The triblock copolymer of the previous procedure was dissolved in 250 mL methanol and 5.17 mL (11.9 g, 83.9 mmol, 4.5 eq.) methyl iodide were added. Then the reaction mixture was heated to 70° C. under reflux. After 24 hours the methanol and the residual methyl iodide were removed in vacuum. The successful quaternization of the tertiary amine groups was verified via the proton shift in the1H NMR of the methylene protons of the ethyl moieties. The molecular weights and polydispersities PDI (Mw/Mn) reported in Table 1 were determined by size exclusion chromatography using dimethyl formamide as eluent and polystyrene as calibration standard.

Table 1 provides an overview of amphiphilic triblock copolymers prepared.

TABLE 1Overview of the synthesized amphiphilic triblock copolymers:Hydrophilic MacroinitiatorDiblock CopolymerEOPOGlycidylTriblock copolymercontentcontentMnamineMnHydrophobicMnRouteNr.(mol %)(mol %)(g/mol)PDImonomer(g/mol)PDImonomer(g/mol)PDI(catalyst)P1100018901.04DEGA21201.05PO36001.05AP2100021201.05DEGA24301.05PO47001.05AP3100018901.04DEGA20901.05PO43901.05AP610009401.05DEGA11601.05PO23101.05AP11100019701.04DEGA20201.06PO31901.06AP12100019701.04DBGA20701.08PO21301.12AP13100018901.07DBGA22801.08PO32501.13AP14100018901.07DBGA22301.11PO34801.14AP15100018901.07PyGA23301.06PO34601.10AP16100018901.07PyGA23301.07PO34701.10AP17100018901.07DEGA30801.06EHGE38001.19AP20100018901.07DEGA21001.05PO33701.12BP22100018901.07PyPA19701.07PO33401.12BP23*100018901.07DEGA30101.19PO30501.15BP24*100018901.07PyGA40301.18PO41301.13BP25100019601.04DEGA21301.06BO33101.05BP26100019601.04DEGA21001.05BO36101.06AP27100019601.04PyGA20001.07BO34301.08AP28100019601.04PyGA19701.05BO31001.11BP31901021401.07DEGA26201.08PO38401.09A

In the block copolymers the second block is located between the first block and the third block. Samples P23 and P24 have a different block sequence. In these samples the third block is located between the first block and the second block (mPEG-block-PPO-block-PDEGA and mPEG-block-PPO-block-PPyGA).

Table 2 provides an overview of quaternized amphiphilic triblock copolymers prepared.

TABLE 2Overview of the quaternized amphiphilic block copolymers:Sample of amphiphilicQuaternizationNr.tri block copolymerreagentQ1P1MelQ2P2MelQ3P3MelQ6P6MelQ11P14MelQ12P15MelQ13P16MelQ14P17MelQ15P20MelQ16P22MelQ17P23*MelQ18P24*MelQ19P25Mel

Synthesis of Amphiphilic Triblock Copolymer Having Ester Units in the Non-Polar Block

Polyester Synthesis with the Diblock Copolymer Macroinitiator

In a 250 mL Schlenk flask, 37.0 g (15.9 mmol, 1.00 eq.) of the diblock copolymer mPEG-PDEGA as described above were dissolved in 30 mL benzene and the mixture was dried via azeotrope distillation of the benzene for 12 h at 60° C. under reduced pressure. Then 31.8 mL (32.7 g, 287 mmol, 18.0 eq.) freshly distilled and dried c-caprolactone were added under inert gas atmosphere and 0.46 mL (0.58 g, 1.43 mmol, 0.005 eq.) tin(II)-octanoate were added. The mixture was heated at 120° C. until full conversion of lactone monomer was reached. The full conversion was verified via1H NMR spectroscopy and SEC measurements.

Table 3 provides an overview of amphiphilic triblock copolymers having ester units:

Diblock CopolymerHydrophilic MacroinitiatorGlycidylTriblock copolymerEOMnamineMnHydrophobicMn(mol %)(g/mol)PDImonomer(g/mol)PDImonomer(g/mol)PDIPE110019601.04DEGA20301.06CL40101.48PE210019601.04DEGA21401.06CL/VL (3:1)37901.40PE310019601.04DEGA21401.06CL/VL (1:1)36901.36PE410019601.04DEGA21501.06L-Lactide24801.42
CL in Table 3 represents c-caprolactone, VL represents δ-valerolactone. The ratios of CL and VL are molar ratios.

Synthesis of Isocyanate-functional Non-polar Block

0.25 mol (500 g) of polypropylenegycol monobutylether (Mn 2000 g/mol) was added over 2 hours at room temperature to 0.62 mol (108.75 g) of 2,4-toluene diisocyanate (TDI). The temperature was held below 45° C. After the end of the addition, stirring was continued for 2.5 h. The excess isocyanate was removed by vacuum (0.1 mbar) distillation from 150 to 170° C. The NCO content was 2.36%, the free TDI content <0.5%.

Synthesis of the Amphiphilic Triblock Copolymer Via Isocyanate Coupling

In a 250 mL Schlenk-flask, 30.0 g (12.5 mmol, 1.00 eq.) of the diblock copolymer mPEG-PDEGA of polymer P1 described above and 22.4 g Bu-PPO—NCO of step 4.1 (NCO-value=2.36%, 12.5 mmol, 1.00 eq.) were mixed and stirred under inert gas atmosphere at 95° C. for 24 h. The successful coupling was verified via SEC measurements.

The results are summarized in Table 4 below:

Diblock CopolymerGlycidylTerblock copolymeramineMnHydrophobicMnNr.monomer(g/mol)PDIbuilding block(g/mol)PDIPX2DEGA21601.05PPO43-NCO32801.23PX3PyGA19801.06PPO43-NCO27401.25

Use of the polymers of the invention as additive for production of pigment concentrates and use thereof in varnish systems

TABLE 5Starting MaterialsSetal 1715 VX-74Saturated polyester, manufacturer: ALLNEXSetamine US-138 BB-70Partly butylated melamine,manufacturer: ALLNEXParaloid B-66*Thermoplastic acrylate resin,50% in Xylolmanufacturer: DOW ChemicalsLaropal A 81 60%Aldehyde resin, manufacturer: BASFMacrynal SM 515 (70%)Hydroxyl functional acrylic resin,manufacturer: ALLNEXDesmodur N 75Aliphatic polyisocyanate (HDI biuret),manufacturer: COVESTROSetalux 1756 VV-65Thermosetting hydroxylated acrylic copolymer,manufacturer: ALLNEXWalsroder NC-ChipsNitrocellulose mixture with plasticizer,E510 ESOmanufacturer: DOW ChemicalsSynthalat E405Short-oil non-drying alkyd resin,60% Xylolmanufacturer: SYNTHOPOLDowanol PMAPropylene glycol methyl ether acetate,manufacturer: Dow ChemicalsShellsol ASolvent naphtha, light aromatic, C9 and C10DIDPDiisodecylphthalatHostaperm Violet ER02Quinacridone pigment (P.V. 19),manufacturer: CLARIANTSpezial schwarz 4Carbon black pigment (P. Bk. 7), manufacturer:ORION Engineered Carbons GmbHPaliogen ® Maroontransparent organic pigment PR 179 (perylene),L 3920manufacturer: BASFCarbon Black FW 200Carbon black pigment (P. Bk. 7),manufacturer: Orion EngineeredCarbons GmbHRaven 5000 UltraCarbon black pigment for high jetness,III beadsmanufacturer: Birla CarbonHostaperm Pink EQuinacridone red (P.R. 122),manufacturer: ClariantBayferrox Red 130MIron oxide red (P.R. 101),manufacturer LanxessBYK-052Silicone-free defoamer, manufacturer:BYK-Chemie GmbHBYK-300Polyether modified polydimethylsiloxane,manufacturer: BYK-Chemie GmbHBYK-306Substrate wetting agent, manufacturer:BYK-Chemie GmbHBYK-310Substrate wetting agent, manufacturer:BYK-Chemie GmbHGaramite 7305Benzalkonium Sepiolite (and) BenzalkoniumMontmorillonite, manufacturerBYK-Chemie GmbH
System 1: Saturated Polyester-Melamine Baking System
Production of the Millbases Based on Saturated Polyester Resin

The Setal 1715 resin, solvent, dispersing additive and pigment were weighed into 100 mL glass bottles to obtain 50 g millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

TABLE 6Composition of the Saturated Polyester millbases:SP 1SP 2(black)(violet)Setal 1715 VX-7412.114.6Spezial schwarz 46.0Hostaperm Violet ER026.0PMA28.928.2Dispersing Additive3.01.2Total Pigment content (%)1212Dispersant (% s.o.p.)5020
Grinding Conditions

Equipment: Lau Disperser DAS 200

Dispersing Time: 180 min, air cooling power at level 3

Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

Evaluation of the viscosity of compositions was assessed using grades: 1 (low viscous), 2 (viscous), 3 (sheer thinning), 4 (high viscous), 5 (not flowable).

Production of the Saturated Polyester Letdown System

Setal 1715 VX-74, Setamine US 138 BB-70, solvent and surface additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

TABLE 7Composition of the Saturated Polyester Letdown System:Setal 1715 VX-74400Setamine US 138 BB-70210Shellsol A108Butyl glycol acetate30BYK-3102
Production of the Pigmented Saturated Polyester Top Coats

The Saturated Polyester Letdown System and the Saturated Polyester millbase were weighed into a PE cup and mixed with a spatula. Subsequently, the completed Setal 1715 Top Coat systems were homogenized in an ANDALOK shaker for 10 min.

TABLE 8Composition of the Pigmented SaturatedPolyester Top Coat SystemsSetalSetal1715-T11715-T2Saturated Polyester15.015.0Letdown SystemSP 1 (black)2.0SP 2 (violet)5.0Pigment content (%)1.43.0
Application and Evaluation of the Pigmented Saturated Polyester Top Coat Systems

The pigmented saturated polyester top coat systems were bar-coated onto a Polyethylene terephthalate (PET) film (50 μm). After a flash-off time of 15 min, the films were cured in the oven at 140° C. for 15 min. Subsequently, gloss was measured with a BYK micro haze plus instrument at an angle of 20°. In each case, high values for gloss are considered to be positive results, as they are generally a sign for an even and homogenous distribution of well dispersed pigment in the coating. In addition, the optical color intensity and transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable).

TABLE 9Setal 1715-T1Setal 1715-T2(black)(violet)Viscos-GlossTrans-Viscos-GlossTrans-Sampleity20°parencyity20°parencycontrol38553815P21881Q218831892P31881Q318821892Q61852Q1218731892P161872Q1318741892P221882Q1618832882P231882-32-3824Q1718852-3824-5P2418732-3834-5Q1818852-3844P251851Q1918832862P261861P271871P281871PX21871PX31873

Viscosity ratings in Table 8 relate to the viscosity of the mill bases. The control sample was prepared without wetting and dispersing additive.

System 2: Thermoplastic Acrylate Resin

Production of Millbases Based on a Thermoplastic Acrylate Resin

The Paraloid B-66 resin, solvent, dispersing additive and pigment were weighed into 100 mL glass bottles to obtain 50 g millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

TABLE 10Composition of the TPA millbases:TPA 1TPA 2(black)(red)Paraloid B-66 (50% in20.515.5xylene)Carbon Black FW 2003.0Perylen Red Paliogen ®6.0Maroon L 3920Dispersing Additive2.11.5n-Butanol5.05.0Butyl acetate:Xylene (1:1)19.422.0Total Pigment content (%)612Dispersant (% s.o.p.)7025
Grinding Conditions

Equipment: Lau Disperser DAS 200

Dispersing Time: 180 min, air cooling power at level 3

Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

Evaluation of the millbase viscosity was assessed using grades: 1 (thin viscous), 2 (viscous), 3 (sheer thinning), 4 (high viscous), 5 (not flowable).

Production of the TPA-Based Letdown System:

Paraloid B-66, solvent, surface additive and plasticizer were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

TABLE 11Composition of the TPA Letdown System:Paraloid B-66 (50% in xylene)705n-Butanol140Shellsol A47Xylene47DIDP60BYK-3061
Production of the Pigmented TPA Letdown System

The TPA letdown system and the TPA-based millbases were weighed into a PE cup and mixed with a spatula. Subsequently, the completed letdown systems were homogenized in an ANDALOK shaker for 10 min.

TABLE 12Composition of the Pigmented TPA Letdown SystemsTPA-B1TPA-B2TPA letdown system15.015.0TPA 1 (black)5.0TPA 2 (red)5.0Pigment content (%)1.53.0
Application and Evaluation of the Pigmented TPA Letdown System

The pigmented TPA letdown system were bar-coated onto a PET film (50 μm) and dried at 22° C. for 24 h. Subsequently, gloss was measured with a BYK micro haze plus instrument at an angle of 20°. In each case, high values for gloss are considered to be positive results. In addition, the optical color intensity and transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable).

TABLE 13TPA-B1TPA-B2(black)(red)Viscos-GlossTrans-Viscos-GlossTrans-Sampleity20°parencyity20°parencycontrol54343705P128033713P218014723Q227834622P318013733Q327933773P62-37933763P1128013722P232-37944673Q172-37452605P242-3754-54663Q182-37452545P252801Q192-3793P262791P272801P282801PX22803

Viscosity ratings in Table 12 relate to the viscosity of the mill bases. The control sample was prepared without wetting and dispersing additive.

System 3: Two-Component Acrylic-Isocyanate Coating

Production of Millbases Based on an Aldehyde Resin

The Laropal A81 resin, solvent, dispersing additive, pigment and optionally Garamite 7305 were weighed into 100 mL glass bottles to obtain 50 g millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

TABLE 14Composition of the aldehyde resin (AR) millbases:AR 1AR 2AR 3(black)(pink)(red)Laropal A81 (60%)16.711.510.1PMA27.330.510.1Dispersing Additive2.02.02.1Raven 5000 Ultra III4.0beadsHostaperm Rosa E6.0Bayferrox 130M27.5Garamite 73050.2Total Pigment81255content (%)Dispersant (% s.o.p.)50337.5
Grinding Conditions

Equipment: Lau Disperser DAS 200

Dispersing Time: 180 min for Laropal 3, 240 min for Laropal 1 and Laropal 2, air cooling power at level 3

Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

Evaluation of the millbase viscosity was assessed using grades: 1 (thin viscous), 2 (viscous), 3 (sheer thinning), 4 (high viscous), 5 (not flowable).

Production of the Letdown for Two-Component Acrylic-Isocyanate Coating

Marcynal SM 515, solvent and surface additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

TABLE 15Composition of the letdown for the Two-Component Acrylic-Isocyanate Coating:Marcynal SM 515 (70%)750Shellsol A128Butylacetate120BYK-3002
Production of the Pigmented Two-Component Acrylic-Isocyanate Top Coats

The letdown and the aldehyde resin based millbases were weighed into a PE cup and mixed with a spatula. Subsequently, all the mixtures were homogenized in an ANDALOK shaker for 10 min. Afterwards, the Desmodur N-75 was added and the pigmented 2 component Acrylic-Isocyanate top coats were homogenized in an ANDALOK shaker for 2 min.

TABLE 16Composition of the Pigmented 2 ComponentAcrylic-Isocyanate Top CoatsTC AI 1TC AI 2TC AI 3Clear Coat15.015.012.5AR 1 (black)4.5AR 2 (pink)6.6AR 3 (red)3.0Desmodur N 755.05.04.5Pigment content (%)1.4538
Application and Evaluation of the Pigmented Two-Component Acrylic-Isocyanate Top Coats
TC Al 1 (Black) and TC Al 2 (Pink):

The pigmented two-component Acrylic-Isocyanate top coats were bar-coated onto a PET film (50 μm). After a flash-off time of 30 min, the films were cured in the oven at 60° C. for 30 min. Subsequently. Subsequently, haze was measured with a BYK micro haze plus instrument at an angle of 20°. Transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable).

TC Al 3 (Red):

The pigmented two-component Acrylic-Isocyanate top coats were bar-coated onto a contrast chart (100 μm). After a while, when film become tacky, a Rub-Out Test was performed. The films were cured in the oven at 60° C. for 30 min. Subsequently, haze was measured with a BYK micro haze plus instrument at an angle of 20°. Low values for haze are considered to be positive results. In addition, the ΔE-values—comparing the color values of rubbed vs. non-rubbed surface—were measured by using a BYK Spectro Guide Sphere d8. Low values for ΔE are considered to be positive results.

TABLE 17TC AITC AI 2TC AI 3(black)(Pink)(red)SampleHazeTranspHazeTranspHazeΔEControl134125131.00P1101100.60Q1122110.36P2101133100.78Q2102121110.41P3101113100.73Q3101121130.53
System 4: Acrylic-Melamine Baking Finish
Production of Millbases Based on an Aldehyde Resin

Usage of the aldehyde resin millbases previously produced: AR 1, AR 2 and AR 3

Production of the Letdown for the Acrylic-Melamine Baking Finish

Setalux 1756 VV-65, Setamine US 138 BB-70, solvent and surface additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

TABLE 18Composition of the letdown for theAcrylic-Melamine Baking Finish:Setalux 1756 VV-65600Setamine US 138 BB-70240Shellsol A80Xylene78BYK-3102
Production of the Pigmented Acrylic-Melamine Baking Finish Top Coats

The letdown for the Acrylic-Melamine Baking Finish and the aldehyde resin based millbases were weighed into a PE cup and mixed with a spatula. Subsequently, the completed Acrylic-Melamine baking finish top coat systems were homogenized in an ANDALOK shaker for 10 min.

TABLE 19Composition of the Pigmented Acrylic-Melamine Baking Finish Top CoatsAM BF 1AM BF 2AM BF 3Clear Coat15.015.017.0AR 1 (black)3.3AR 2 (pink)5AR 3 (red)3.0Pigment content (%)1.4538
Application and Evaluation of the Acrylic-Melamine Baking Finish Top Coats
AM BF 1 (Black) and AM BF 2 (Pink):

The pigmented Acrylic-Melamine Baking Finish Top Coats were bar-coated onto a PET film (50 μm). After a flash-off time of 15 min, the films were cured in the oven at 140° C. for 25 min. Subsequently, haze was measured with a BYK micro haze plus instrument at an angle of 20°. Transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable). Transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable).

BF 3 (Red):

The pigmented Acrylic-Melamine Baking Finish Top Coats were bar-coated onto a contrast chart (100 μm). After a while, when film become tacky, Rub-Out Tests were performed. The films were cured in the oven at 140° C. for 25 min. Subsequently, haze was measured with a BYK micro haze plus instrument at an angle of 20°. Low values for haze are considered to be positive results. In addition, the ΔE-values—comparing the color values of rubbed vs. non-rubbed surface —were measured by using a BYK Spectro Guide Sphere d8. Low values for ΔE are considered to be positive results.

TABLE 20AM BF 1 (black)AM BF 2 (pink)AM BF 3 (red)SampleHazeTransp.HazeTransp.HazeΔEControl135215471.04P1101P2101Q2103162190.56P3101Q3121162180.50