DICYCLOPENTADIENE MODIFIED ESTER OLIGOMERS USEFUL IN CORROSION RESISTANT COATINGS

Abstract

Corrosion resistance coatings and dicyclopentadiene modified ester oligomers useful in corrosion resistant coatings. The corrosion resistant coatings exhibit improved corrosion resistance, proved adhesion, lower toxicity, unlimited pot life, and/or lower volatile organic compounds (VOCs).

Claims

1. A coating composition, comprising at least one dicyclopentadiene modified ester oligomer and at least one ethylenically unsaturated monomer, wherein said at least one dicyclopentadiene modified ester oligomer comprises at least one dicyclopentadiene and at least one diol, and wherein said coating composition is curable to a surface by at least one of oxidative curing and thermal curing.

2. The coating composition of claim 1, wherein said at least one dicyclopentadiene modified ester oligomer further comprises a dicarboxylic acid.

3. The coating composition of claim 1, wherein said at least one ethylenically unsaturated monomer is selected from the group consisting of trimethylolpropane trimethacrylate (TMPTMA); trimethylolpropane triacrylate (TMPTA); triethyleneglycol dimethacrylate (TRGDMA); and monoacryloxyethyl succinate (MAES).

4. The coating composition of claim 2, wherein said at least one ethylenically unsaturated monomer is selected from the group consisting of trimethylolpropane trimethacrylate (TMPTMA); trimethylolpropane triacrylate (TMPTA); triethyleneglycol dimethacrylate (TRGDMA); and monoacryloxyethyl succinate (MAES).

5. The coating composition of claim 3, further comprising a metal drier.

6. A dicyclopentadiene modified ester oligomer of formula (I), wherein R is a hydrocarbon group comprising 1 to 20 carbon atoms, R is a hydrocarbon group comprising 1 to 20 carbon atoms, R is a hydrocarbon group comprising 1 to 20 carbon atoms, and x is H or CH.sub.3 ##STR00001##

7. The dicyclopentadiene modified ester oligomer of claim 6, wherein R comprises 6 carbon atoms, R comprises 10 carbon atoms, R comprises 2 carbon atoms, and x is H.

8. The dicyclopentadiene modified ester oligomer of claim 6, wherein R comprises 6 carbon atoms, R comprises 10 carbon atoms, R comprises 2 carbon atoms, and x is CH.sub.3.

9. A coating composition, comprising the dicyclopentadiene modified ester oligomer of claim 7 and at least one ethylenically unsaturated monomer.

10. A coating composition, comprising the dicyclopentadiene modified ester oligomer of claim 8 and at least one ethylenically unsaturated monomer.

11. The coating composition of claim 9, wherein said at least one ethylenically unsaturated monomer is selected from the group consisting of trimethylolpropane trimethacrylate (TMPTMA); trimethylolpropane triacrylate (TMPTA); triethyleneglycol dimethacrylate (TRGDMA); and monoacryloxyethyl succinate (MAES).

12. The coating composition of claim 10, wherein said at least one ethylenically unsaturated monomer is selected from the group consisting of trimethylolpropane trimethacrylate (TMPTMA); trimethylolpropane triacrylate (TMPTA); triethyleneglycol dimethacrylate (TRGDMA); neopentyl glycol, propoxylated (2 mol), diacrylate (NPGO2DA); tripropylene glycol diacrylate (TPGDA); and monoacryloxyethyl succinate (MAES).

13. The coating composition of claim 11, further comprising a metal drier.

14. The coating composition of claim 12, further comprising a metal drier.

15. The coating composition of claim 13 or claim H, wherein said coating composition is curable to a surface by at least one of oxidative curing and thermal curing.

Description

DESCRIPTION OF DRAWINGS

[0011] FIG. 1 is a diagram depicting a generic two-step process for preparing dicyclopentadiene modified ester oligomers. In step A, maleic anhydride is reacted with water to yield maleic acid which then reacts with dicyclopentadiene to produce maleic acid-dicyclopentadiene half-ester. In step B, the maleic acid-dicyclopentadiene half-ester is reacted with one or more diols and optionally one or more dicarboxylic acids to yield dicyclopentadiene modified ester oligomers. R is a hydrocarbon that comprises 1 to 20 carbon atoms, preferably 3 to 8 carbon atoms. R is a hydrocarbon that comprises 1 to 20 carbon atoms, preferably 3 to 8 carbon atoms. n is 0 to 10, preferably 0 to 3.

[0012] FIG. 2 is a diagram depicting the generic formula for a dicyclopentadiene modified ester urethane oligomer. R is a hydrocarbon that comprises 1 to 20 carbon atoms, preferably 3 to 8 carbon atoms. R is a hydrocarbon that comprises 1 to 20 carbon atoms, preferably 8 to 12 carbon atoms. R is a hydrocarbon that comprises 1 to 20 carbon atoms, preferably 1 to 3 carbon atoms. x is CH.sub.3 or H.

[0013] FIG. 3 is a diagram depicting a generic four-step process for preparing dicyclopentadiene modified polyester urethane oligomers. In step A, maleic anhydride is reacted with water to yield maleic acid which then reacts with dicyclopentadiene to produce maleic acid-dicyclopentadiene half-ester. In step B, the maleic acid-dicyclopentadiene half-ester is reacted with one or more diols and one or more dicarboxylic acids to yield a hydroxy functional dicyclopentadiene modified ester oligomers. In step C, a hydroxy functional acrylate monomer is added to a diisocyanate at elevated temperature. In step D, the hydroxy functional dicyclopentadiene modified ester oligomer is added to the acrylated diisocyanate of step C. R is a hydrocarbon that comprises 1 to 20 carbon atoms, preferably 3 to 8 carbon atoms. R is a hydrocarbon that comprises 1 to 20 carbon atoms, preferably 3 to 8 carbon atoms. R is a hydrocarbon that comprises 1 to 20 carbon atoms, preferably 6 to 12 carbon atoms. R is a hydrocarbon that comprises 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. n is 0 to 10, preferably 0 to 3. m is 1 or 2.

DEFINITIONS

[0014] To facilitate understanding of the invention, a number of terms are defined herein.

[0015] The term oxidative curing means the re-association of electrons inherent in carbon-carbon double bonds to produce a cross-linked network via a peroxide-initiated mechanism and/or an oxygen gas-initiated mechanism. Examples of oxidative curing include but are not limited to peroxide-initiated curing of a fiberglass resin and air-drying of an alkyd resin.

[0016] The term thermal curing means the re-association of electrons inherent in carbon-carbon double bonds to produce a cross-linked network via a heat-initiated mechanism. An example of thermal curing includes but is not limited to an oven-curing of a resin.

[0017] The term metal drier means a ligand of a common inorganic metal. Metal driers include but are not limited to organic salts of cobalt, organic salts of zirconium, and organic salts of calcium.

DESCRIPTION OF INVENTION

[0018] In one embodiment, the coating composition comprises a dicyclopentadiene modified ester oligomer mixed with an ethylenically unsaturated monomer, a metal dryer, and a solvent. The ethylenically unsaturated monomer can be trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), triethyleneglycol dimethacrylate (TRGDMA), monoacryloxyethyl succinate (MAES), or a combination of TMPTA and TRGDMA. The metal dryer can be cobalt, zirconium, or calcium, or preferably all three. The solvent can be methyl ethyl ketone (MEK), toluene, or both. In another embodiment, a flow additive can be used.

[0019] In another embodiment, the dicyclopentadiene modified ester urethane oligomer is comprised of hydroxy-functional dicyclopentadiene ester oligomer (HDEO), an isocyanate, and a hydroxy-functional acrylate monomer (HAM). HDEOs are formed by reacting dicyclopentadiene, water, maleic anhydride, one or more glycols, and one or more monofunctional epoxide monomers. The one or more glycols includes but is not limited to 1,6 hexanediol (HDO); 1,4 butanediol (BDO); pentaerythrtiol; neopentyl glycol (NPG); diethylene glycol (DEG), trietheylene glycol; tetraetheylene glycol; 1,2 propanediol (PG); 1,3-propanediol (PDO); glycerine; and 2-methyl, 1,3-propanediol (MPD); and trimethylol propane (TMP). The one or more monofunctional epoxide monomers includes but is not limited to C12-C14 aliphatic monoglycidyl ether, 2-ethylhexyl glycidyl ether, cresyl glycidyl ether, para-tert butylphenol glycidyl ether, and glycidyl neodecaneoate. Isocyanate includes but is not limited to aliphatic monomeric or polymeric diisocyanates such as isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (HMDI), and hexamethylene diisocyanate (HDI) and trimers thereof, and aromatic monomeric or polymeric diisocyanates such as 2,4-2,6 toluene diisocyanate (TDI), diphenylmethane diisocyanates (MDI), and trimers thereof. HAM includes but is not limited to hydroxy ethyl acrylate, hydroxy methyl acrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, and ethoxylated or propoxylated versions thereof. In a preferred embodiment, the HDEO is 2,5-furandione, polymer with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-inden-5(or 6)-yl ester, ester with 2,3-dihydroxypropyl neodecanoate, which is the reaction product of dicyclopentadiene, water, maleic anhydride, trimethylolpropane, and glycidyl neodecaneoate; the isocyanate is isophorone diisocyanate; and the HAM is hydroxy ethyl acrylate.

[0020] In another embodiment, the HDEOs are formed by reacting dicyclopentadiene, water, maleic anhydride, one or more glycols, one or more monofunctional epoxide monomers, and one or more dicarboxylic acids. The one or more dicarboxylic acids includes but is not limited to succinic acid, adipic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic anhydride, dodecanedioc acid, and methyl esters thereof.

[0021] In another embodiment, the coating composition comprises a dicyclopentadiene modified ester urethane oligomer mixed with an ethylenically unsaturated monomer, a metal dryer, and a solvent. The ethylenically unsaturated monomer can be trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), triethyleneglycol dimethacrylate (TRGDMA), monoacryloxyethyl succinate (MAES), or a combination of TMPTA and TRGDMA. The metal dryer can be cobalt, zirconium, or calcium, or preferably all three. The solvent can be methyl ethyl ketone (MEK), toluene, or both. In another embodiment, a flow additive can be used.

[0022] The coating compositions can be cured to a surface by oxidative curing or thermal curing. The coating compositions can be applied to a variety of surfaces including but not limited to metal, concrete, wood, plastic, ceramic, textile, leather, paper, rubber, and glass to improve the corrosion resistance of the surface. The method for applying the coating compositions includes but is not limited to spraying, roll coating, curtain coating, and smoothing with a smoothing device such as a bird bar or Meyer rod. The method for applying can be manual, automated, or a combination thereof.

[0023] The optimal final thickness of the applied coating composition varies depending on, without limitation, the surface, the contour of the surface, the formula of the coating composition, the solvent content (if any), and the means of curing. A typical final thickness of the applied coating composition is less than or equal to 100 mils (2.54 mm), but can vary depending on the previously mentioned factors.

[0024] The cured coating compositions can be evaluated using techniques well-known in the art. Although the degree of curing is easily measured through certain qualitative methods such as fingernail marring or film integrity after thumb twist, a number a quantitative measures of curing efficiency are possible. For example, the measurement of disappearance of acrylate carbon-carbon double bonds at 1636 cm.sup.1 using Fourier transform infrared spectroscopy is the gold standard in assessing the curing efficiency. Similar techniques can be applied to measure the disappearance of maleate carbon-carbon double bonds and allylic carbon-carbon double bonds at varying cm1 ranges. In addition, a number of other quantitative tests such as cross-hatch adhesion, tape adhesion, flexibility, hardness, and impact resistance can be used to quantify the curing efficiency and the suitability of the coating compositions.

[0025] In all embodiments, the dicyclopentadiene modified ester oligomer and/or dicyclopentadiene modified ester urethane oligomer can be made without solvent.

EXAMPLES

Example 1

Synthesis of Dicyclopentadiene Modified Ester Oligomers

[0026] Six batches of dicyclopentadiene modified ester oligomers were synthesized.

[0027] Batch 1 was prepared by adding 846 g of dicyclopentadiene (Sigma Aldrich, St. Louis, Mo., USA) to 121 g of water under nitrogen and heating the mixture to 80 C. 627 g of maleic anhydride (Sigma Aldrich, St. Louis, Mo., USA) was gradually added to the mixture of dicyclopentadiene and water under nitrogen and was held at 125 C. for 2 hours. At the end of the 2-hour incubation, 486 g of 1,3-propanediol (DuPont, Wilmington, Del., USA), 378 g of succinic acid (Myriant, Woburn, Mass., USA or Kawasaki Kasei Chemicals, Kawasaki City, Kanagawa, Japan), and 43 g of trimethylol propane (Alfa Aesar, Haverhill, Mass., USA) were added and gradually heated to 205 C. The final acid value was 24.7 mg KOH/g of sample.

[0028] Batch 2 was prepared by adding 1010 g of dicyclopentadiene to 44 g of water under nitrogen and heating the mixture to 80 C. 747 g of maleic anhydride (Sigma Aldrich, St. Louis, Mo., USA) was gradually added to the mixture of dicyclopentadiene and water under nitrogen and was held at 125 C. for 2 hours. At the end of the 2-hour incubation, 619 g of 1,3-propanediol, 378 g of succinic acid, and 43 g of trimethylol propane were added and gradually heated to 205 C. The final acid value was 5.6 mg KOH/g of sample. This batch contained hydroxy functional groups suitable for urethane synthesis.

[0029] Batch 3 was prepared by adding 140 g of dicyclopentadiene to 20 g of water under nitrogen and heating this mixture to 80 C. 104 g of maleic anhydride was gradually added to the mixture of dicyclopentadiene and water under nitrogen and was held at 125 C. for 2 hours. At the end of 2-hour incubation, 69 g of ethylene glycol (Sigma Aldrich, St. Louis, Mo., USA), 63 g of succinic acid, and 7 g of trimethylol propane were added and gradually heated to 205 C. The final acid value was 24.1 mg KOH/g of sample.

[0030] Batch 4 was prepared by adding 126 g of dicyclopentadiene to 18 g of water under nitrogen and heating this mixture to 80 C. 93 g of maleic anhydride was gradually added to the mixture of dicyclopentadiene and water under nitrogen and was held at 125 C. for 2 hours. At the end of 2-hour incubation, 101 g of diethylene glycol (SABIC, Riyadh, Saudi Arabia), 56 g of succinic acid, and 6 g of trimethylol propane were added and gradually heated to 205 C. The final acid value was 24.9 mg KOH/g of sample.

[0031] Batch 5 was prepared by adding 133 g of dicyclopentadiene to 19 g of water under nitrogen and heating this mixture to 80 C. 103 g of maleic anhydride was gradually added to the mixture of dicyclopentadiene and water under nitrogen and was held at 125 C. for 2 hours. At the end of 2-hour incubation, 90 g of 1,4-butanediol (Sigma Aldrich, St. Louis, Mo., USA), 59 g of succinic acid, and 7 g of trimethylol propane were added and gradually heated to 205 C. The final acid value was 25.0 mg KOH/g of sample.

[0032] Batch 6 was prepared by adding 135 g of dicyclopentadiene to 19 g of water under nitrogen and heating this mixture to 80 C. 97 g of maleic anhydride was gradually added to the mixture of dicyclopentadiene and water under nitrogen and was held at 125 C. for 2 hours. At the end of 2-hour incubation, 79 g of 1,3-propanediol, 73 g of adipic acid (Sigma Aldrich, St. Louis, Mo., USA), and 7 g of trimethylol propane were added and gradually heated to 205 C. The final acid value was 25.5 mg KOH/g of sample.

Example 2

Mixing of Coating Composition Containing Dicyclopentadiene Modified Ester Oligomers

[0033] In a mixing cup, the polyester dicyclopentadiene oligomer was warmed to 60 C. with the appropriate monomer(s). The mixture was then stirred with mechanical agitation until homogenous. If necessary, the entire mixture was re-warmed and re-agitated until 100% homogeneous.

Example 3

Synthesis of Dicyclopentadiene Modified Ester Urethane Oligomers

[0034] To a 1L reaction flask equipped with nitrogen blanket, agitation, temperature control and a condenser, 312 g of DCPD and 45 g of water were charged and warmed to 80 C. To this 232 g of maleic anhydride was added slowly in order to control exotherm under 125 C. Once all maleic was added, 211 g of trimethylol propane was added and heated to 205 C. The reaction was held until the acid value was measured to be 13.0 mg KOH/g of sample. Subsequently, the reactor was cooled to 120 C. and 46 g glycidyl neodecanoate was added. The reactor was held at 120 C. until the acid value was 0.5 mg KOH/g of sample. The final hydroxyl value was measured to be 142.8 mg KOH/g of sample.

[0035] Subsequently, in a 1 L reaction flask equipped with a dry air sparge, agitation, a condenser and a drop funnel, 96 g IPDI was charged to said flask and warmed to 70 C. To this, 50 g of hydroxy ethyl acrylate was added slowly to control exotherm. Finally, 168 g of the reaction product in the previous paragraph as well as 135 g of isobornyl acrylate were added. The reaction was allowed to proceed to completion under agitation and heat.

[0036] To a 3 L reaction flask equipped with nitrogen blanket, agitation, temperature control and a condenser, 1008 g of DCPD and 145 g of water were charged and warmed to 80 C. To this 748 g of maleic anhydride was added slowly in order to control exotherm under 125 C. Once all maleic was added, 617 g of 1,3-propanediol was added and heated to 205 C. The reaction was held until the acid value was measured to be 3.2 mg KOH/g of sample. The final hydroxyl value was measured to be 148.7 mg KOH/g of sample.

[0037] Subsequently, in a 1 L reaction flask equipped with a dry air sparge, agitation, a condenser and a drop funnel, 228 g IPDI was charged to said flask and warmed to 70 C. To this, 133 g of hydroxy ethyl methacrylate was added slowly to control exotherm. Finally, 359 g of the reaction product in the previous paragraph as well as 80 g of diethylene glycol dimethacrylate (DEGDMA) was added. The reaction was allowed to proceed to completion under agitation and heat.

[0038] To a 1 L reaction flask equipped with nitrogen blanket, agitation, temperature control and a condenser, 977 g of DCPD and 140 g of water were charged and warmed to 80 C. To this 725 g of maleic anhydride was added slowly in order to control exotherm under 125 C. Once all maleic was added, 860 g of trimethylol propane was added and heated to 205 C. The reaction was held until the acid value was measured to be 11.5 mg KOH/g of sample. Subsequently, the reactor was cooled to 120 C. and 128 g glycidyl neodecanoate was added. The reactor was help at 120 C. until the acid value was 1.5 mg KOH/g of sample. The final hydroxyl value was measured to be 142.8 mg KOH/g of sample.

[0039] Subsequently, in a 2 L reaction flask equipped with a dry air sparge, agitation, a condenser and a drop funnel, 293 g IPDI was charged to said flask and warmed to 70 C. To this, 153 g of hydroxy ethyl acrylate was added slowly to control exotherm. Finally, 464 g of the reaction product in the previous paragraph as well as 390 g of isobornyl acrylate were added. The reaction was allowed to proceed to completion under agitation and heat.

Example 4

Mixing of Coating Composition Containing Dicyclopentadiene Modified Ester Urethane Oligomers

[0040] In a mixing cup, the urethane dicyclopentadiene oligomer was warmed to 60 C. with the appropriate monomer(s). The mixture was then stirred with mechanical agitation until homogenous. If necessary, the entire mixture was re-warmed and re-agitated until 100% homogeneous.

Example 5

Testing of Coating Compositions

[0041]

TABLE-US-00001 TABLE 1 Experimental results of coatings applied to metal panels and cured via oxidative curing. Koenig Cross Mandrel Impact Resistance Hardness Hatch Bend Test (in-lbs) Test Adhesion Test (cm) Intrusion Extrusion (seconds) Test Sample 1 3 6 <6 144 1 Sample 2 3 25 <6 106 4 Sample 3 3 6 <6 110 5 Sample 4 3 15 <6 100 5 Mandrel Bend Test scoring: 3 to 24, where 3 is no coating delamination and 24 is total coating delamination; measured according to ASTM D522. Impact Resistance Test measure according to ASTM D2794. Koenig Hardness Test was measured using ASTM D4366. Cross Hatch Adhesion Test scoring: 1 to 5, where 1 is total coating delamination and 5 is no coating delamination; measured according to ASTM D3359.

TABLE-US-00002 TABLE 2 Compositions of coating samples applied to metal panels and cured via oxidative curing. Sample 1 Sample 2 Sample 3 Sample 4 DMEO (percentage) 70 100 70 50 Ethylenically unsaturated 30 monomer 1 (percentage) Ethylenically unsaturated 30 monomer 2 (percentage) Alkyd resin (percentage) 50 Cobalt (parts per hundred) 0.44 0.44 0.44 0.44 Zirconium (parts per hundred) 0.44 0.44 0.44 0.44 Calcium (parts per hundred) 1.32 1.32 1.32 1.32 Solvent 1 (parts per hundred) 25 25 25 25 Solvent 2 (parts per hundred) 25 25 25 25 Ethylenically unsaturated monomer 1 is DEGDMA. Ethylenically unsaturated monomer 2 is Miramer 5C6641 (Miwon North America, Exton, Pennsylvania, USA). Alkyd resin is Deltech 440-50M (Deltech Corporation, Baton Rouge, Louisiana, USA). Solvent 1 is toluene. Solvent 2 is methyl ethyl ketone.

TABLE-US-00003 TABLE 3 Experimental results of coatings applied to metal panels and cured via oxidative curing. Creep Test Field Blister Blister (mean creep from Rust Size Density scribe in mm) Test Test Test Sample 5 4 10 0 0 Sample 6 4 10 0 0 Sample 7 <1 10 0 0 Sample 8 <1 10 0 0 Sample 9 3 10 0 0 Sample 10 2 10 0 0 Field Rust Test scoring: 0 to 10, where 0 is greater than 50% rust and 10 is less than 0.01% rust; measured according to ASTM B117. Blister Size Test scoring: 2 to 8, where 2 is the largest size blister and 8 is the smallest size blister; 0 indicates no blister; measured according to ASTM B117. Blister Density Test scoring: 0 to 4, where 0 is no blisters and 4 is dense blisters; measured according to ASTM B117.

TABLE-US-00004 TABLE 4 Compositions of coatings applied to metal panels and cured via oxidative methods Sample Sample Sample Sample Sample Sample 5 6 7 8 9 10 DMEO (percentage) 70 35 70 70 70 DMEUO (percentage) 35 Ethylenically unsaturated 30 30 15 monomer 3 (percentage) Ethylenically unsaturated 30 15 monomer 4 (percentage) Ethylenically unsaturated 30 monomer 5 (percentage) Alkyd resin (percentage) 100 Cobalt (parts per hundred) 0.44 0.44 0.44 0.44 0.44 0.44 Zirconium (parts per hundred) 0.44 0.44 0.44 0.44 0.44 0.44 Calcium (parts per hundred) 1.32 1.32 1.32 1.32 1.32 1.32 Silicone (drops) 4 4 4 4 4 4 Solvent 1 (parts per hundred) 10 10 10 10 10 10 Solvent 2 (parts per hundred) 10 10 10 10 10 10 Ethylenically unsaturated monomer 3 is triethylene glycol dimethacrylate. Ethylenically unsaturated monomer 4 is trimethyol propane triacrylate. Ethylenically unsaturated monomer 5 is trimethylol prpane trimethacrylate. Alkyd resin is Deltech 440-50M. Solvent 1 is toluene. Solvent 2 is methyl ethyl ketone.