Coating compositions comprising a compound with at least two cyclic carbonate groups and a siloxane group

Abstract

Coating compositions comprising a compound having at least two cyclic carbonate groups and a siloxane group (called “carbonate compound”).

Claims

1. A coating composition, comprising: a carbonate compound of formula III ##STR00008## wherein R.sup.2 to R.sup.4 are independently hydrogen or an organic group comprising 1 to 10 C atoms, K is a divalent organic group comprising 2 to 10 C atoms, R.sup.5 and R.sup.6 are independently a hydrogen atom or an organic group comprising 1 to 10 C atoms, and m is an integer of from 1 to 99.

2. The coating composition according to claim 1, which comprises from 0.1 to 50 wt% of the carbonate compound.

3. The coating composition according to claim 1, further comprising: a reactive compound comprising at least two reactive groups selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group.

4. The coating composition according to claim 3, wherein the reactive compound comprises a polyester polyol, a polyether polyol, a polyesteramide polyol, a polycarbonate polyol, a polyacrylate polyol, a polyetheramine, a polyamidoamine, or any mixture thereof.

5. A method for producing a coated substrate, the method comprising: applying a coating composition to a substrate, wherein the coating composition comprises a carbonate compound comprising at least two cyclic carbonate groups and a siloxane group, a reactive compound comprising at least two reactive groups selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group, and thereafter reacting the carbonate compound with the reactive compound.

6. A coating composition, comprising: a carbonate compound comprising at least two cyclic carbonate groups and a siloxane group, wherein the carbonate compound is obtained by hydrosilylation of a compound of formula IV ##STR00009## wherein radicals R1* to R4* are independently hydrogen or an organic group comprising 1 to 10 C atoms, but at least one of the radicals R1* to R4* comprises an ethylenically unsaturated group with a siloxane which comprises at least two silicon-bonded hydrogen atoms.

7. The coating composition according to claim 6, wherein the compound of the formula IV is a compound in which R.sup.1* is a C2 to C10 alkenyl group or a C2-C10 alkynyl group, and R.sup.2*, R.sup.3* and R.sup.4* are independently a hydrogen atom or a C1 to C10 alkyl group.

8. The coating composition according to claim 6, wherein R.sup.1* in the formula IV is a vinyl group.

9. The coating composition according to claim 6, wherein the compound of the formula IV is a compound in which R.sup.1* is a vinyl group, R.sup.2* is a C1 to C4 alkyl group, and R.sup.3* and R.sup.4* are an H atom.

10. The coating composition according to claim 6, which comprises from 0.1 to 50 wt % of the carbonate compound.

11. The coating composition according to claim 6, further comprising: a reactive compound comprising at least two reactive groups selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group.

12. The coating composition according to claim 11, wherein the reactive compound comprises a polyester polyol, a polyether polyol, a polyesteramide polyol, a polycarbonate polyol, a polyacrylate polyol, a polyetheramine, a polyamidoamine, or any mixture thereof.

13. A coating composition, comprising a carbonate compound comprising at least two cyclic carbonate groups and a siloxane group, and a reactive compound comprising at least two reactive groups selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group; and wherein the reactive compound comprises a polyester polyol, a polyether polyol, a polyesteramide polyol, a polycarbonate polyol, a polyacrylate polyol, a polyetheramine, a polyamidoamine, or any mixture thereof.

14. The coating composition according to claim 13, wherein the carbonate compound comprises from two to fifty cyclic carbonate groups and a siloxane group comprising 2 to 100 silicon atoms.

15. The coating composition according to claim 13, wherein the carbonate compound is a compound of formula III ##STR00010## wherein R.sup.2 to R.sup.4 are independently hydrogen or an organic group comprising 1 to 10 C atoms, K is a divalent organic group comprising 2 to 10 C atoms, R.sup.5 and R.sup.6 are independently a hydrogen atom or an organic group comprising 1 to 10 C atoms, and m is an integer of from 1 to 99.

16. The coating composition according to claim 13, wherein the carbonate compound is obtained by hydrosilylation of a compound of formula IV ##STR00011## wherein radicals R1* to R4* are independently hydrogen or an organic group comprising 1 to 10 C atoms, but at least one of the radicals R1* to R4* comprises an ethylenically unsaturated group with a siloxane which comprises at least two silicon-bonded hydrogen atoms.

17. The coating composition according to claim 16, wherein the compound of the formula IV is a compound in which R.sup.1* is a C2 to C10 alkenyl group or a C2-C10 alkynyl group, and R.sup.2* , R.sup.3* and R.sup.4* are independently a hydrogen atom or a C1 to C10 alkyl group.

18. The coating composition according to claim 16, wherein R.sup.1* in the formula IV is a vinyl group.

19. The coating composition according to claim 16, wherein the compound of the formula IV is a compound in which R.sup.1* is a vinyl group, R.sup.2* is a C1 to C4 alkyl group, and R.sup.3* and R.sup.4* are an H atom.

20. The coating composition according to claim 13, which comprises from 0.1 to 50 wt % of the carbonate compound.

21. A carbonate compound of formula III ##STR00012## wherein R.sup.2 to R.sup.4 are independently hydrogen or an organic group comprising 1 to 10 C atoms, K is a divalent organic group comprising 2 to 10 C atoms, R.sup.5 and R.sup.6 are independently a hydrogen atom or an organic group comprising 1 to 10 C atoms, and m is an integer of from 1 to 99.

Description

EXAMPLES

Preparation Examples

Preparation Example 1

Preparation of 4-methyl-4-vinyl-5-methylene-1,3-dioxolan-2-one (Compound of the Formula IV, for Short: exoVCA)

(1) ##STR00006##

(2) A 300 ml autoclave is charged with 3-methylpent-1-ene-4-yn-3-ol (100.00 g, 1.04 mol), triphenylphosphane (2 g, 8 mmol), tetraethylammonium bromide (2 g, 8 mmol) and copper(II) acetate (0.5 g, 2.8 mmol). The mixture is then heated to 75° C. and 20 bar of CO.sub.2 are injected. The mixture is stirred at 75° C. for 15 hours, then cooled to room temperature and let down to atmospheric pressure. This batch is run a total of nine times, and the combined reaction discharges are jointly distilled (conditions: 10 mbar, bath temperature 100° C., 20 cm Vigreux column. The product goes over at a temperature of about 68° C.). This gives 1042 g (79%) of product with a purity of 98.5% (GC area %).

(3) NMR analysis: conforms to the analysis indicated in the literature (e.g., in Tetrahedron 65 (2009) 1889-1901).

Preparation Example 2

Preparation of a Compound of Formula 1 from tetramethyldisiloxane and exoVCA (for Short: Si-V 1)

(4) ##STR00007##

(5) A 500 ml three-neck flask is charged under an argon atmosphere with 4-methyl-4-vinyl-5-methylene-1,3-dioxolan-2-one (210.6 g, 1.5 mol) and Pt/Al2O3 (5% Pt on Al203, 5.0 g, 1.3 mmol). The mixture is heated to 60° C. and then 1,1,3,3-tetramethyldisiloxane (95.06 g, 0.71 mol) is added in portions over the course of one hour. In this case an exothermic reaction with slight evolution of gas is observed (internal temperature climbs to 68° C.). After the end of the addition, the mixture is first stirred at 70° C. for 16 hours, then at 85-90° C. for 5 hours. After cooling to room temperature, the solidified reaction discharge is dissolved in 300 ml of toluene at 60° C. and the catalyst is removed hot by filtration. The toluene is removed under reduced pressure (50° C., 20 mbar) and the residue is dissolved in 1500 ml of n-hexane at 70° C., then cooled to 10° C. The colorless solid is isolated by filtration and washed with n-hexane (200 ml) and dried. The product is obtained as a colorless solid (222 g, 73%). GC purity: 99.6 area %; melting point: 80-82° C.

(6) 1H NMR (CDCl3, 500.1 MHz)=4.81 (d, br, 2H), 4.27(d, br, 2H), 1.81-1.87 (m, 2H), 1.64-1.70 (m, 2H), 1.58 (s, 6H), 0.48-0.61 (m, 4H), 0.07 (s, 12H).

(7) 13C NMR (CD2Cl2, 125.8 MHz)=157.8, 151.8, 88.5, 85.7, 34.9, 26.0, 11.2, 0.1. 29Si NMR (CDCl3, 99.4 MHz)=8.1.

(8) Besides the use of Pt/Al2O3 as catalyst, as described here, the following other Pt catalysts may also be employed: Pt/C and PtO2.

Preparation Example 3

Preparation of a Compound of Formula 1 from Crosslinker V58 and exoVCA (for Short: Si-V 2)

(9) An autoclave is charged under an inert gas atmosphere with 4-methyl-4-vinyl-5-methylene-1,3-dioxolan-2-one (10.00 g, 0.07 mol), Pt/Al2O3 (5% Pt on Al2O3, 0.5 g) and Wacker® crosslinker V58 (46 g). The crosslinker V58 from Wacker comprises polysiloxane with a high number of silicon-bonded hydrogen atoms. The mixture is heated to 75° C. and stirred at this temperature for 10 hours. It is then cooled to room temperature and 1-hexene (100 ml) is added. The mixture is stirred at 100° C. for 10 hours. After the solution has been filtered and the filtrate concentrated under reduced pressure (25 mbar, 50° C.), the product is obtained with a viscose consistency (55 g). It is used in the polymer synthesis without further purification and characterization. Characterization: the reaction was monitored by 1H NMR spectroscopy until the vinyl group signal characteristic of the reactant had disappeared.

Preparation Example 4

Preparation of a Compound of Formula 1 from Crosslinker V90 and exoVCA (for Short: Si-V 3)

(10) A three-neck flask is charged under an inert gas atmosphere with 4-methyl-4-vinyl-5-methylene-1,3-dioxolan-2-one (10.0 g, 0.07 mol), Pt/Al2O3 (5% Pt on Al2O3, 0.5 g) and Wacker® crosslinker V90 (46 g). The crosslinker V90 from Wacker comprises polysiloxane with a high number of silicon-bonded hydrogen atoms. The mixture is heated to 85° C. and stirred at this temperature for 6 hours. It is then cooled to room temperature and 1-hexene (59 g) is added.

(11) The mixture is stirred at 50° C. for 4 hours. After the solution has been filtered and the filtrate concentrated under reduced pressure (25 mbar, 50° C.), the product is obtained with a viscose consistency (49 g). It is used in the polymer synthesis without further purification and characterization.

(12) Use Examples

(13) 1.) Coating Composition Comprising Si-V 1 and polyol.

(14) 10 g of Joncryl 500 (polyacrylatol), 4.14 g of Si-V 1, and 0.141 g of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene, catalyst) were combined in 6 ml of butyl acetate and mixed at room temperature until the resulting mixture was uniform.

(15) Joncryl® 500 is a commercially available polyacrylatol having a glass transition temperature Tg of −7° C., an OH number of 140 mg KOH/g, and an equivalent weight OH of 400 (this means:

(16) 1 mol OH to 400 g of the polyacrylatol)

(17) Joncryl 500 is in the form of an 80% strength by weight solution in MAK.

(18) The resulting mixture was applied with a wet film thickness of 250 μm to the respective substrate (glass for determining the hardness, and Bonder panel (Gardobond®) for determining the elasticity and the adhesion (cross-cut)), left to evaporate at room temperature for 15 minutes, and then cured for 30 minutes in a drying oven at the stated temperature (see Table 1). For subsequent crosslinking, the cured film was stored overnight in a conditioning chamber, after which the typical paint parameters were ascertained.

(19) The Erichsen cupping was determined in analogy to DIN 53156 by the pressing of a metal ball into the uncoated side of the panel. High values denote high flexibility. The value determined is the value at which the coating exhibits the first crack.

(20) The pendulum damping was determined in accordance with DIN 53157 on glass. High values denote high hardness.

(21) The cross-cut test (G for short) tests the adhesion. The test took place likewise on Bonder panel. In the cross-cut test, the surface of the cured paint is incised with a lattice and observed to determine whether the paint undergoes delamination at the incision edges. Delamination is assessed visually with the scores of 0 (no delamination) to 5 (marked delamination). The lower the score, the better the adhesion.

(22) The results of the performance tests are found in Table 1.

(23) TABLE-US-00001 TABLE 1 Pendulum Erichsen hardness cupping Curing at Example [sec] [mm] Appearance G [° C./min] 1 18 >9.5 clear, specks 0 100° C. 2 18 >9.5 clear, specks 0 120° C. 3 18 >9.5 clear, specks 0 140° C.

(24) 2.) Coating Composition comprising Si-V 3 and polyol.

(25) Joncryl® 945 is a commercially available polyacrylatol having a glass transition temperature Tg of 17° C., an OH number of 180 mg KOH/g, and an OH equivalent weight of 310 (this means: 1 mol OH to 310 g of the polyacrylatol)

(26) Joncryl 945 is in the form of a 76% strength by weight solution in n-butyl acetate.

(27) Sovermol 8151® is a commercially available biobased polyol having an OH equivalent weight of 260.

(28) Desmophen 650 MPA® is a commercially available branched polyester from Bayer MaterialScience, having a solids content of 65 wt % in MPA (1-methoxypropyl acetate). The hydroxyl group content is reported as 5.3 wt %.

(29) For the determination of the pot life, Si-V 3, the respective polyol (Table 2), and DBU as catalyst were mixed in the quantities indicated, and a determination was made of the time after which there was a marked increase in viscosity and the mixture was no longer fluid.

(30) TABLE-US-00002 TABLE 2 Pot lives Catalyst Polyol Type Si—V3 DBU Pot life Example and amount [g] [g] [min] 4 Joncryl 500; 2.5 g 4.0 0.035 20 5 Joncryl 945; 2.0 g 4.0 0.035 20 6 Joncryl 500; 1.25g 2.0 0.00875 45 7 Joncryl 945; 1.0 g 2.0 0.00875 35 8 Desmophen 650 MPA; 0.8 g 2.0 0.00875 >120 9 Sovermol 815; 0.65 g 2.0 0.00875 30 10 Joncryl 500; 1.25 g 2.0 0.00583 >120 11 Joncryl 945; 1.0 g 2.0 0.00583 >120 12 Desmophen 650 MPA; 0.8 g 2.0 0.00583 >120 13 Sovermol 815; 0.65 g 2.0 0.00583 >120

(31) 3.) Coating Composition Comprising Si-V 2 and amines

(32) 4.61 g of Si-V 2 were mixed with 0.2 g of isophoronediamine (IPDA) and 0.28 g of Jeffamine D 230® until the resulting mixture was uniform. No accompanying catalyst was used.

(33) For the determination of the performance properties, the resulting mixture was applied as described above to glass or Bonder panel in a wet film thickness of 250 μm, left to evaporate at room temperature for 15 minutes, and then cured for 2×60 minutes in a drying oven at 100° C. For subsequent crosslinking, the cured film was stored overnight in a conditioned chamber, after which the typical paint parameters were ascertained.

(34) Jeffamine D 230® is a commercially available polyetheramine from Huntsman, as diamine. (The manufacturer reports Jeffamine D 230 to have a weight-average molar weight of 230 and an average number of 2.5 repeating propylene glycol units).

(35) With regard to performance tests, the details stated above are applicable. In addition the chemical resistance was tested.

(36) The test for resistance to exposure to chemicals was carried out in a method based on DIN 68861-1, using a 1:1 mixture of ethanol and ethyl acetate and an exposure time of 10 seconds. The damage to the paint surface was assessed visually with the scores of 0 (no damage) to 5 (paint dissolves and can be wiped away). The lower the score, the better the resistance toward chemicals.

(37) The results of the performance tests are found in Table 3.

(38) TABLE-US-00003 Pendulum Erichsen Chemicals hardness cupping Appearance, Example test [sec] [mm] comments G 14 0 32 7.8 Smooth, 53 μm 0 film thickness

(39) Si-V 2 was mixed with various amines and the pot lives were determined as described above.

(40) The amines used are m-xylenediamine (MXDA), isophoronediamine (IPDA), Jeffamine D 230, or mixtures thereof. The amines were used in different molar ratios to the Si-V 2.

(41) Results are found in Table 4.

(42) TABLE-US-00004 TABLE 4 Pot lives Amine Type Si—V2 Pot life Example and amount [g] [min] 15 IPDA; 0.34 g 3.09 <5 16 MXDA; 0.28 g 3.20 0 17 Jeffamine D 230; 0.48 g 3.19 20 18 IPDA; 0.23 g 2.63 <5 19 MXDA; 0.12 g 2.76 0 20 Jeffamine D 230; 0.38 g 3.07 15 21 IPDA; 0.20; 4.61 5 Jeffamine D 230; 0.28 g