Coating composition or sealant comprising a compound with a five-membered cyclic monothiocarbonate group

Abstract

A process for preparing coatings or sealed materials using a coating composition or a sealant that contains a first component and a second component. The first component includes a compound A) with at least one five-membered cyclic monothiocarbonate group. The second component includes a compound B) with at least one amino group. The at least one amino group can be a primary or secondary amino group or blocked primary or secondary amino group. Compounds A) or B) may additionally have at least one polymerizable, ethylenically unsaturated group. The coating composition or sealant may further include a compound C) with at least one polymerizable, ethylenically unsaturated group.

Claims

1. A process comprising: preparing a coating or sealed material using a coating composition or a sealant, wherein the coating composition or the sealant comprises: a first component which comprises a compound A) with at least one five-membered cyclic monothiocarbonate group, and a second component which comprises a compound B) with at least one amino group, selected from the croup consisting of a primary amino group, a secondary amino group, a blocked primary amino group, and a blocked secondary amino group wherein compound A) or compound B) optionally have at least one polymerizable, ethylenically unsaturated group, and wherein the coating composition or the sealant optionally comprises compound C) with at least one polymerizable, ethylenically unsaturated group.

2. The process according to claim 1, wherein compound A) is a compound of formula I ##STR00027## with R.sup.1a to R.sup.4a independently from each other representing hydrogen or an organic group with up to 50 carbon atoms whereby, alternatively, R.sup.2a, R.sup.4a and the two carbon atoms of the thiocarbonate group, together, form a five to ten membered carbon ring, or a compound of formula II ##STR00028## with R.sup.1b to R.sup.4b independently from each other representing hydrogen or an organic group with up to 50 carbon atoms whereby, alternatively, R.sup.2b, R.sup.4b and the two carbon atoms of the monothiocarbonate group, together, form a five to ten membered carbon ring, and with one of the groups R.sup.1b to R.sup.4b being a linking group to Z, n representing an integral number of at least 2 and Z representing a n-valent organic group.

3. The process according to claim 1, wherein the coating composition or the sealant comprises at least one compound A), compound B), or compound C) with at least one polymerizable, ethylenically unsaturated group.

4. The process according to claim 1, wherein one of compound A) or compound B) comprises at least one polymerizable, ethylenically unsaturated group.

5. The process according to claim 2, wherein compound A) and compound B) do not comprise a polymerizable, ethylenically unsaturated group and the coating composition or the sealant comprises compound C).

6. The process according to claim 1, wherein compound A) is liquid at 21° C., 1 bar.

7. The process according to claim 6, wherein the liquid state of compound A) is obtained by dissolving compound A) which is solid at 21° C., 1 bar into compound A which is liquid at 21° C., 1 bar.

8. The process according to claim 1, wherein the coating composition or the sealant comprises 0.8 to 1.2 mol of the at least one amino group of compound B) per 1 mol of the at least one five-met bored cyclic monothiocarbonate group of compound A).

9. The process according to claim 1, wherein the coating composition or the sealant comprises 5 to 500 parts by weight of pigments or fillers per 100 parts by weight of compound A), compound B), and compound C).

10. The process according to claim 1, wherein the coating composition is applied to a surface and cured to obtain a coating with a thickness of 0.01 to 10 millimeter

11. The process according to claim 1, wherein the sealant is applied to a gap or cavity and cured to obtain a sealed material.

12. A compound A) of formula III ##STR00029## wherein G represents an aldylene group with 2 to 10 carbon atoms.

13. A compound A) of formula ##STR00030##

Description

EXAMPLES

Test Methods

[0202] Pendulum Hardness

[0203] The coating composition is coated on a glass plate at room temperature and stored at room temperature for 6 days. Thereafter they were kept at 60° C. for 5 days. The pendulum hardness was determined by the method of Koenig on glass plates (DIN EN ISO 1522).

[0204] In Table 3 the number of oscillations is listed.

[0205] Cross-Cut

[0206] The cross-cut was determined in accordance with DIN EN ISO 2409 on a Bonder panel. The obtained coatings were first kept at room temperature for 6 days. Thereafter they were kept at 60° C. for 5 days. The curing was followed by conditioning at 23±2° C. and 50±10% humidity for one day (1 d) or seven days (7 d). The adhesion of the coating to the panel was judged pursuant to a scale of 0 to 100%. with 100% standing for “no detachment of the coating layer observed” and 0 standing for “full detachment”.

[0207] Erichsen Deep Drawing

[0208] The Erichsen deep drawing was determined according to DIN EN ISO 20482/DIN EN ISO 1520. The Erichsen deep indicates the flexibility of the coating. Fur such purpose the coating is subjected to bending stresses in a bending tester.

[0209] The coating composition is coated on a metal plate at room temperature and stored at room temperature for 6 days. Thereafter they were kept at 60° C. for 5 days. The coated side of the metal plate is deformed by a punch with a defined pressure. On the other side of the metal plate a bulge is formed. The depth of the bulge when first cracks become visible in the coating is a measure of elasticity of the coating. Values for the depth of the bulge are reported in millimeter (mm) in Table 3.

[0210] Following compounds have been used in the examples:

Compound A:

Bis-1,3-Oxathiolan-2-one, 5,5′[1,4-butanediylbis(oxymethylene)] of formula

[0211] ##STR00020##

1,2-Cyclohexanedicarboxylic acid, 1,2-bis[2-oxo-1,3-Oxathiolan-5-yl] ester of formula

[0212] ##STR00021##

Compound B:

1,3-Bis(aminomethyl)cyclohexane of formula

[0213] ##STR00022##

Compound C:

Di-hydroxyethylmethacrylat-trimethylhexyl-dicarbamate of formula

[0214] ##STR00023##

Bisphenol A-glycerolat-dimethacrylat

[0215] ##STR00024##

Trimethylolpropane Trimethacrylate

Synthesis of bis-1,3-oxathiolan-2-one, 5,5′[1,4-butanediylbis(oxymethylene)] of formula

[0216] ##STR00025##

First Step: Phosgenation of 1,4-butanediolbisglycidylether

[0217] Into a 2 L stirred tank glas reactor equipped with two condensers (−30° C. and −78° C. (dry ice)) phosgene dip pipe and internal thermometer 980 g (4.60 mol, 1.00 eq.) 1,4-butanediolbisglycidylether were introduced under an atmosphere of nitrogen. After the addition of the starting material the cooling of the tank reactor was turned on and was adjusted to 15° C. After the reactor reached this temperature, 13.5 g (0.0490 mol, 1.00 mol %) tetrabutylammonium chloride (TBACl) were added. After solvation of the TBACI gaseous phosgene (overall 1011 g, 10.2 mol, 2.22 eq.) was added to the reactor via the dip pipe. The temperature of the reaction mixture was continuously monitored and was kept below 25° C. by carefully adjusting the rate of the phosgene addition. Overall the phosgene addition took approximately 10 h. After the phosgene addition was completed the initial cooling of the reactor was replaced by slight heating (30° C.). The reaction mixture was stirred at this temperature for 2 h. Afterwards the reaction mixture was stripped, with nitrogen at 30° C., phosgene-free overnight. The resulting colorless, slightly viscous oil (1834 g, 4.59 mol, >99% yield, regioisomeric purity: ca. 95%) was directly used, without further purification, for the thiocarbonate formation.

Second Step: Reaction With Sulfur Compound

[0218] The respective β-chloroalkyl chloroformiate ([2-chloro-1-[4-(3-chloro-2-chlorocarbonyloxypropoxy)butoxymethyl]ethyl] carbonochloridate) (845 g, 2.1 mol) and dichloromethane (2.5 L) are placed in a 8 L reactor. The solution was cooled down to 0° C. before Na2S (2 equiv., 15 wt % aqueous solution) was slowly added, maintaining the temperature at 5° C. After the complete addition the reaction mixture was allowed to warm to room temperature. The phases were separated and the aqueous phase was extracted with dichloromethane (0.5 L). The solvent was removed from the combined organic phases under reduced pressure. The viscous oil was redisolved in 0.3 L dichloromethane and filtered over Celite. After removal of the solvent under reduced pressure the desired product was obtained a as a clear viscous oil (656 g, 96%).

Synthesis of 1,2-cyclohexanedicarboxylic acid, 1,2-bis[2-oxo-1,3-oxathiolan-5-yl] ester

[0219] ##STR00026##

First Step: Phosgenation of bis(2,3-epoxpropyl)-cyclohexan-1,2-dicarboxylate

[0220] Into a 250 ml stirred tank glas reactor equipped with two condensers (−30° C. and −78° C. (dry ice)) phosgene dip pipe and internal thermometer 115 g (0.404 mol, 1.00 eq.) Bis(2,3-epoxpropyl)-cyclohexan-1,2-dicarboxylate were introduced under an atmosphere of nitrogen. After the addition of the starting material, 2.20 g (8.00 mmol, 1 mol %) tetrabutylammonium chloride (TBACl) were added. After solvation of the TBACl gaseous phosgene (overall 100 g, 1.01 mol, 2.50 eq.) was added to the reactor via the dip pipe. The temperature of the reaction mixture was continuously monitored and was kept below 40° C. by carefully adjusting the rate of the phosgene addition. Overall the phosgene addition took approximately 4 h. After the phosgene addition was completed, the reaction mixture was heated to 45° C. and stirred for further 2 h. Afterwards the reaction mixture was stripped, with nitrogen at 45° C., phosgenefree overnight. The resulting colorless, highly viscous oil (179 g, 0.370 mol, 92% yield, regioisomeric purity: ca. 95%) was directly used, without further purification, for the thiocarbonate formation.

Second Step: Reaction With Sulfur Compound

[0221] The β-chloroalkyl chloroformiate (bis(3-chloro-2-chlorocarbonyloxy-propyl) cyclohexane-1,2-dicarboxylate) (320 g, 0.66 mol) and dichloromethane (0.8 L) are placed in a 4 L reactor. The solution was cooled down to 0° C. before Na2S (2 equiv., 15 wt % aqueous solution) was slowly added, maintaining the temperature at 5° C. After the complete addition the reaction mixture was allowed to warm to room temperature. The phases were separated and the aqueous phase was extracted with dichloromethane (0.5 L). The solvent was removed from the combined organic phases under reduced pressure. The viscous oil was redisolved in 0.3 L dichloromethane and filtered over Celite. After removal of the solvent under reduced pressure the desired product was obtained a as a clear viscous oil (240 g, 74%).

Example 1

[0222] Bis-1,3-Oxathiolan-2-one, 5,5′[1,4-butanediyIbis(oxymethylene)] [5 g] and Bisphenol A-glycerolat-dimethacrylat (CAS 1565-94-2) [7.9 g] were mixed under stirring at room temperature. Subsequently, 1,3-Bis(aminomethyl)cyclohexane [2.2 g] was added and stirring was continued for additional 20 min at room temperature, increasing viscosity over time. The reaction mixture was transferred to coating application via doctor blade (60 mu) using various substrates:

[0223] glass

[0224] steel

[0225] polycarbonate (PC)

[0226] A homogeneous film could be applied to the various substrates. The samples were cured at room temperature until they were completely dry (t<24 h)

Example 2

[0227] Bis-1,3-Oxathiolan-2-one, 5,5′[1,4-butanediyIbis(oxymethylene)] [5 g], Trimethylolpropane trimethacrylate [1.75 g] and Di-HEMA-trimethylhexyl dicarbamate (CAS 72869-86-4, Isomeric mixture) [3.65 g] were mixed under stirring at room temperature. Subsequently, 1,3-Bis(aminomethyl)cyclohexane [2.2 g] was added and stirring was continued for additional 20 min at room temperature, increasing viscosity over time. The reaction mixture was transferred to coating application via doctor blade (60 mu) using various substrates:

[0228] glass

[0229] steel

[0230] polycarbonate (PC)

[0231] A homogeneous film could be applied to the various substrates. The samples were cured at room temperature until they were completely dry (t<48 h).

Example 3

[0232] Bis-1,3-Oxathiolan-2-one, 5,5′[1,4-butanediyIbis(oxymethylene)] [5 g], Trimethylolpropane trimethacrylate [3.49 g] were mixed under stirring at room temperature. Subsequently, 1,3Bis(aminomethyl)cyclohexane [2.2 g] was added and stirring was continued for additional 20 min at room temperature, increasing viscosity over time. The reaction mixture was transferred to coating application via doctor blade (60 mu). Substrates:

[0233] glass, steel.

[0234] A homogeneous film could be applied to the various substrates. The samples were cured at room temperature until they were completely dry (t<48 h).

Example 4

[0235] 1,2-Cyclohexanedicarboxylic acid, 1,2-bis[2-oxo-1,3-Oxathiolan-5-yl] ester [5 g], Trimethylolpropane trimethacrylate [2.78 g] were mixed under stirring at room temperature. Subsequently, 1,3Bis(aminomethyl)cyclohexane [2.1 g] was added and stirring was continued for additional 3 min, increasing viscosity over time. The reaction mixture was transferred to coating application via doctor blade (60 mu) employing glass, steel and PC substrates.

[0236] The coatings were completely dry after 90 min at room temperature.

TABLE-US-00003 TABLE 3 properties of coatings Pendulum Hardness Cross-cut Erichsen oscillations test % mm Example 1 142 100 10.8 Example 2 78 90 >11 Example 3 23 80 10.2 Example 4 125 95 10.1