ULTRAVIOLET CURABLE EPOXIDIZED ALKYDS

Abstract: The epoxidation of alkyds containing anhydrides or diacids with cycloaliphatic unsaturation results in epoxy resins which cure rapidly in UV light to produce uniform films without the use of flow modifiers. The fatty acid portion of the alkyd functions as an internal plasticizer. Crosslinking occurs through oxirane rings in both the anhydride and fatty acid moieties of the alkyd to produce hard, but not brittle films. Excellent water resistance is obtained without thermal post curing.

Description: ULTRAVIOLET CURABLE EPOXIDIZED ALKYDS BACKGROUND OF THE INVENTION This invention relates to solventless, internally plasticized epoxy compositions which cure rapidly in ultraviolet light. A suitable photoinitiator, such as triphenylsulfonium hexafluorophosphate [(φ)- 3 S + PF 6 ], is required. Sunlight or UV lamps may be used as radiation sources. The mechanism of cure is cationic rather than free radical. When a photon strikes the photoinitiator, a strong acid (HPF 6 ) is generated. This acid initiates crosslinking through oxirane rings resulting in a network polymer. A comparison of this invention with related technologies is shown in Table I. Table I Comparison Conventional Conventional Cycloaliphatic Invention Alkyd Epoxy Epoxy Number of Components One Two One (plus One (plus pho¬ (plus drier) photoinitiator) toinitiator) Cure Type Autoxidation Chemical UV UV Cure Mechanism Free Radical Addition Cationic Cationic Cure Time Moderate to slow Moderate to slow Rapid Rapid Latent Cure Yes No Yes Yes Solvent Use Yes Yes No No Externally Plasticized No No Yes No Internally Plasticized Yes Yes No Yes (by fatty acid) (by curing agent) (by faπy acid) Conventional alkyds are oil modified polyesters. Without oil modification, the polyester is a brittle solid. By incorporating unsaturated fatty acids into the polyester, a film with the desired flexibility can be obtained. Alkyds are comprised of an anhydride or diacid, a polyol, and unsaturated fatty acids. Examples of these would be phthalic anhydride, glycerine, and tall oil fatty acid. Vegetable oils, such as soybean oil, contribute both polyol and unsaturated fatty acids to an alkyd formulation. The cure of an alkyd is through autoxidation by a free radical mechanism. The sites of crosslinking are carbons adjacent to unsaturation. Alkyds are one of the most widely used protective coatings due to their durability and relatively low cost. Alkyds typically contain solvents for viscosity reduction. Conventional epoxy resins are multifunctional glycidyl ethers derived from the reaction of bisphenol A and epichlorhydrin. The oxirane rings of these resins react with amine curing agents, such as reactive polyamides, by chemical addition. The resulting polymer is widely used in protective coatings when superior corrosion and water resistance is required. Solvents are used to reduce the viscosity of the two component reaction mixture. Cycloaliphatic epoxy resins, such as (3,4 - epoxycyclohexyl) methyl - 3,4 - epoxycyclohexane carboxylate [ ] have previously been employed as solventless epoxy compositions which cure rapidly in ultraviolet light. These resins produce rigid films without the addition of a plasticizer. A flow modifier is typically added to prevent surface defects. Reactive diluents, such as propylene glycol monomethylether, may be added to reduce the viscosity of the formulation. Cationic polymerization of epoxy resin materials by the use of certain radiation sensitive aromatic oniu salts of Group Via elements was disclosed in U.S. Patent Number 4,058,401 to Crivello. Epoxy resins polymerizable to a higher molecular weight were identified. Examples of photoinitiators identified were tri¬ phenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimoniate, and triphenylsulfonium tetrafluoroborate. Disclosure of this type of photoinitiator was expanded by Crivello in U.S. Patent Number 4, 161 ,478 which specifically addresses triphenylsulfonium hexafluorophosphate. A method for effecting the cationic polymerization of epoxy resins with this type of photoinitiator was disclosed by Crivello in U.S. Patent Number 4, 138,255. Photocopoiymerizable compositions based on epoxy and hydroxyi- containing organic materials were disclosed by Smith in U.S. Patent Number 4,256,828. A process for this polymerization was disclosed by Smith in U.S. Patent Number 4,318,766. Crivello discussed the use of a hydroxy functional flexibilizer in U.S. Patent Number 4,175,972. These patents also involved the use of photosensitive aromatic sulfonium salts. Simultaneous free radical and cationic cure of mixtures of certain oxirane containing and aliphatically unsaturated containing organic resins was addressed by Crivello in U.S. Patent Number 4,245,029. Arylsulfonium salt- solvent mixtures were disclosed as photoinitiators by Crivello in U.S. Patent Number 4,273,668. Propylene carbonate was specifically identified as a solvent. Additional photoinitiators were identified by Crivello in U.S. Patent Numbers 4,407,759 and 4,41 7,061 . General structures for these photoinitiators are , respectively. It is an object of the present invention to produce a durable ultraviolet curable epoxidized alkyd resin coating that cures through a cationic mechanism. It is a further object to produce a durable ultraviolet curable epoxidized alkyd coating that is internally plasticized to produce hard but not brittle films without the use of external plasticizers. It is a further object to produce a durable ultraviolet curable epoxidized alkyd coating which is water resistant without thermal post-curing. It is a further object to produce a durable ultraviolet curable epoxidized alkyd coating which is uniform without the use of flow modifiers. It is an object of the invention to produce a film which is internally plasticized through the use of tall oil fatty acids. These fatty acids act as an internal plasticizer due to their long aliphatic chains. Further, they provide a site for curing by epoxidation of their unsaturation. DESCRIPTION OF THE PREFERRED EMBODIMENTS An epoxidized alkyd prepared from tall oil fatty acid, glycerine, and tetrahydrophthalic anhydride (THPA) is illustrated as follows: or 0 / \ CH 3 -(CH 2 ) 4 -CH-CH-CH 2 -CH-CH-(CH 2 ) 7 - 0 A suitable photoinitiator, such as triphenyl sulfonium hexafluor¬ ophosphate, is mixed with the epoxy resin at a concentration of 3% by weight. This mixture is stable in the absence of UV light. When a photon strikes the photoinitiator, a strong acid is generated which initiates rapid cationic cure through the oxirane rings of the epoxy resin. The use of an epoxy grade of tall oil fatty acid (TOFA), such as ACINTOL ® EPG from Arizona Chemical Company, precludes the need to remove dimethoxystilbene (DMS) from the alkyd with a wiped film evaporator (WFE). When DMS is present during epoxidation of the alkyd, a dark red complex results. Oleic acid, such as EMERSOL ® 221 from the Emery Industries Division of Henkel Corporation, gave similar results to those from ACINTOL ® EPG without a WFE step. Other TOFAs, such as ACINTOL ® FA-2, gave similar results to ACINTOL ® EPG when DMS was removed from the alkyd by WFE distillation. Crosslinking of the oxirane rings in the TOFA or oleic acid moieties of the epoxidized alkyd in addition to cross linking of the cycloaliphatic oxirane rings of the anhydride moiety result in hard, but not brittle films. Glycerine is the preferred polyol of this invention. Trimethylolpropane can be used when a more flexible coating is desired, although a slower cure rate is obtained. Stoichiometric amounts of polyols and acids are used to form the alkyd. A preferred anhydride of this invention is 1 ,2,3,6-tetrahydrophthalic anhydride. The intended applications for this invention are those in which the epoxy resin viscosity can be reduced by heat or by a reactive diluent, such as limonene dioxide. An example would be the coating of optical fibers. Another example would be protective coatings applied by thermal spraying. The following examples are illustrative of alkyd resins and ultraviolet curable epoxidized alkyd resins embodying the invention and are not intended as limiting the scope thereof. EXAMPLE I The preparation of an alkyd of this invention using an epoxy grade of tall oil fatty acid can be accomplished as follows: Charge: 145.5g ACINTOL ® EPG (tall oil fatty acid) 63.2g THPA ( 1 ,2,3,6 - tetrahydrophthalic anhydride) 42.8g Glycerine (96%) (polyol) 0.125g Phosphoric Acid Equipment: 500 ml, 3 neck flask equipped with an agitator, nitrogen inlet thermometer with thermowatch, steam heated precondenser, distilla¬ tion head with * thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, and bubble trap . Procedure: (1 ) Charge all ingredients. (2) Start a nitrogen sweep of the flask. (3) Heat gradually to 220 δ C with agitation. The head temperature should not exceed 100 2 C during heat up. (4) Hold 16 hours at 220^0. (5) Gradually pull a vacuum (25" Hg) at 220 2 C and maintain for 5 - 10 minutes. Break vacuum with N 2 . (6) Cool and analyze. Results: Acid Number 4.3 Color, Gardner 3 + Viscosity, 25 S C 13,360 cps Iodine Value 123 Hydroxyl Value 14 Yield 92.4% EXAMPLE II The preparation of an alkyd of this invention using an oleic acid can be accomplis >h-h_eardl a QsO Charge: 145.5g EMERSOL ® 221 (oleic acid) 63.2g THPA ( 1 ,2,3,6 - tetrahydrophthalic anhydride) 42.8g Glycerine (96%) (polyol) 0.125g Phosphoric Acid Equipment: 500 ml, 3 neck flask equipped with an agitator, nitrogen inlet thermometer with thermowatch, steam heated precondenser, distillation head with thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, and bubble trap. Procedure: (1 ) Charge all ingredients. (2) Start a nitrogen sweep of the flask. (3) Heat gradually to 220 2 C with agitation. The head temperature should not exceed 100 2 C during heat up. (4) Hold 8 hours at 220 2 C. (5) Gradually pull a vacuum (25" Hg) at 220 2 C and maintain for 5 - 10 minutes. Break vacuum with N 2 . (6) Cool and analyze. Results: Acid Number 6.4 Color, Gardner 4 Viscosity, 25 2 C 9,900 cps Iodine Value 99 Hydroxyl Value 14 Yield 90.2% EXAMPLE III The preparation of an alkyd of this invention using a standard grade of tall oil fatty acid can be accomplished as follows: Charge: 145.5g ACINTOL ® FA-2 (tall oil fatty acid) 63.2g THPA ( 1 ,2,3,6 - tetrahydrophthalic anhydride) 42.8g Glycerine (96%) (polyol) 0.125g Phosphoric Acid Equipment: 500 ml, 3. neck flask equipped with an agitator, nitrogen inlet thermometer with thermowatch, steam heated precondenser, distillation head with thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, bubble trap and a wiped film evaporator (WFE). Procedure: (1 ) Charge all ingredients. (2) Start a nitrogen sweep of the flask. (3) Heat gradually to 220 S C with agitation. The head temperature should not exceed 100 2 C during heat up. (4) Hold 16 hours at 220 C. (5) Gradually pull a vacuum (25" Hg) at 220 2 C and main¬ tain for 5 - 10 minutes. Break vacuum with N 2 . (6) Cool and analyze. (7) Pass the reaction mixture through a wiped film evapora¬ tor at 210 2 C under a 0.1 mm Hg vacuum. The reaction mixture should be warmed to facilitate its flow. Results: Before WFE Acid Number 7.1 Color, Gardner 4- Yield 94.3% After WFE Residue Distillate Acid Number 4.0 Acid Number 109 Color, Gardner 3 Color, Gardner 1 1- Viscosity, 25 2 C 13,900 cps Yield 2.4% Iodine Value 123 Hydroxyl Value 19 Yield 97.6% EXAMPLE IV Epoxidation of the alkyds of this invention can be accomplished as follows: Charge: 75. Og Alkyd from Examples 1 &3 75. Og Alkyd from Example 2 150.0g Methylene Chloride 150.0g Methylene Chloride 96.6g Peracetic Acid (32%) 78.2g Peracetic Acid (32%) 2.5g Sodium Acetate 2.0g Sodium Acetate 23. Og Water (distilled) 18.6g Water (distilled) Equipment: 500 ml, 3 neck flask with agitator, N 2 inlet, thermometer with thermowatch, equilibrium addition funnel, ice bath, heating mantle, bubble trap, and separatory funnels. Procedure: ( 1 ) Charge the alkyd and CH 2 CI 2 . (2) Start a nitrogen sweep of the flask. (3) Cool the alkyd solution to 20 2 C with agitation. (4) Dissolve the sodium acetate in water. (5) Add the sodium acetate solution to the peracetic acid. (6) Add the buffered peracetic acid solution dropwise below the surface of the reaction mixture. (7) Allow the reaction mixture to exotherm to 30 2 C, then maintain the temperature at 25-30 2 C. (8) Agitate overnight at 25-30 s C. (9) Pour the reaction mixture into 400 mis of distilled water. ( 10) Separate the organic layer. ( 1 1 ) Extract the water phase with 75 mis of CH 2 CI 2 . (12) Combine the CH 2 CI 2 extract with the organic phase. (13) Wash the organic phase with 2 x 100 ml portions of distilled water. ( 14) Wash the organic phase with 4 x 100 ml portions of 0.1 % Na 2 CO 3 . (15) Wash the organic phase with 100 mis of distilled water. ( 16) Dry the organic phase with Na 2 SO 4 . (17) Remove CH 2 CI 2 under vacuum with a roto-evaporator. Results: Analysis Epoxidized Epoxidized Epoxidized Alkyd Alkyd Alkyd (Example I) (Example II) (Example III) Acid Number 5.0 5.4 5.2 Color, Gardner < 1 < 1 < 1 Viscosity, 25 2 C 26,000 cps 12,200 cps 34,900 cps Iodine Value 0.6 2.6 1.9 Yield 79.2g 79.1 g 79.3g 10 EXAMPLE V A description of the cure and evaluation of the products of this invention is as follows: Cure Ingredients: 10. Og of epoxidized alkyd/0.3g of 3M's FX-512 (photoinitiator) Procedure: The ingredients were mixed well in a 50 ml beaker with a spatula. A 3 mil film was drawn on a cold rolled steel panel with a draw down bar. The film was placed in direct sunlight. EVALUATION OF CURED MATERIAL The panels remained outside for 4-7 days before evaluation. The following results were obtained with films from the alkyds in examples 1-3 after they had been epoxidized as in example 4: Analysis Cured Film From Cured Film From Cured Film From Epoxidized Alkyd Epoxidized Alkyd Epoxidized Alkyd (Example I) (Examole II) (Examole III) Film Appearance Smooth, Glossy Smooth. Glossy Smooth, Glossv Cure Rate 1 " ■ 1 minute aι 1 minute a 1 minute Hardness, Pencil' 1 ' AH 4H 4H Adhesion. Cross Hatch™ 5 5 5 Impact Resistance 1 *' P80F P120F P100F P20R P20R P20R Weatherability"' Yellowing yes yes yes Film deterioration none observed Water Resistance'*' . - No effect Chemical Resistance 1 " HCI (10%) - . No effect NaOH (10%) - - Partial film loss Acetic Acid (5%) . . Darkened, blisters MEK . . No effect CH-CI, . . No effect Methane. - - No effect Ethyl Acetate . . No effect Xylene - . No effect Xylene IPA (50/50) - - No effect Gasoline - - No effect Mineral Oil - . No effect Ethanol (200 proof) . . No effect Ethanol (3A) - - Blisters (1 ) Dry to touch in direct sunlight (2) 8H is hardest → HB (soft) → 6B (very soft) (3) On a scale of 1 - 5, 5 is best (4) p _. pass, F » forward, R - reverse. Highest is 160. Units are in.-lbs. This is a measure of flexibility. (5) After three months of outside exposure. Slight yellowing is evident within days. (6) After six months of water immersion of the panel (7) Seven day chemical spot test EXAMPLE VI The use of Limonene Dioxide (LDO) to reduce the viscosity of an expoxi- dized alkyd is described as follows: Analysis Epoxidized Alkvd Epoxidized Alkvd/LDO (80/20) Viscosity, 25 2 C 31,300 cps 4,060 cps Viscosity, 40 2 C 7,560 cps 1,350 cps Cured Film (Refer to Example V) Analysis Film Appearance Smooth, Glossy Smooth, Glossy Cure Rate ≡ 1 minute ≡ 1 minute Hardness, Pencil 4H 4H Adhesion, Cross Hatch 5 5 Impact Resistance P120F P80F P20R P20R EXAMPLE VII The use of trimethylolpropane (TMP) as the polyol instead of glycerine is described as follows: Alkyd Charge: 145.5g ACINTOL ® EPG (tall oil fatty acid) 63.2g THPA ( 1 ,2,3,6 - tetrahydrophthalic anhydride) 61 .6g Trimethylolpropane (TMP) (polyol) 0.125g Phosphoric Acid Alkyd Equipment and Procedure: Same as Example I Results: Analysis TMP Based Glycerine Based Alkvd Alkvd Acid Number 13.7 4.3 Color, Gardner 3 + 3 + Viscosity, 25 2 C 10,500 cps 13,360 cps Iodine Value 1 14 1 23 Hydroxyl Value 23 14 Yield 89.0% 92.4% Epoxidation: Same as Example IV Epoxidation Results: Analysis TMP Based Glycerine Based Epoxidized Epoxidized Alkyd Alkvd (Examole I) Acid Number 10.1 5.0 Color, Gardner < 1 < 1 Viscosity, 25 S C 22,850 cps 26,000 cps Iodine Value 3.1 0.6 Yield 81.3g 79.2g Cure and Evaluation: Same as Example V Results: Analysis TMP Based Glycerine Based Cured Material Cured Material Film Appearance Smooth, Glossy Smooth, Glossy Cure Rate e 2.5 minutes ≡ 1 minute Hardness, Pencil 2H 4H Adhesion, Cross Hatch 5 5 Impact Resistance P160F P80F P40R P20R An increase in film flexibility is gained at the expense of cure rate. EXAMPLE VIII The use of methyl tetrahydrophthalic anhydride (MTHPA) instead of THPA as a diacid with cycloaliphatic unsaturation is described as follows: Alkyd Charge: 145.5g ACINTOL ® EPG (tall oil fatty acid) 63.2g MTHPA 40.7g Glycerine (96%) (polyol) 0.125g Phosphoric Acid Alkyd Equipment and Procedure: Same as Example III Results: Analysis MTHPA Based Alkvd THPA Based Alkvd Acid Number 1 1.9 4.0 Color, Gardner 2 + 3 Viscosity, 25 2 C 9,300 cps 13,900 cps Iodine Value 120 123 Hydroxyl Value 25 19 Yield 90.5% 92.0% Epoxidation: Same as Example IV Epoxidation Results: Analysis MTHPA Based THPA Based Acid Number 6.3 5.2 Color, Gardner < 1 < 1 Viscosity, 25 2 C 24,500 cps 34,900 cps Iodine Value 2.2 1.9 Yield 82.9g Cure and Evaluation: Same as Example V Results: Analysis MTHPA Based THPA Based Cured Material Cured Material Film Appearance Smooth, Glossy Smooth, Glossy Cure Rate ≡ 1 .5 minutes ≡ 1 minute Hardness, Pencil 4H 4H Adhesion, Cross Hatch 3 5 Impact Resistance P140F PI OOF F20R P20R While the invention has been described and illustrated with specific materials and procedures, it is understood that the invention is not restricted to those employed for this purpose. Numerous variations of such materials and procedures can be employed, as will be appreciated by those skilled in the art.

Claims: WHAT IS CLAIMED IS: 1. An internally plasticized, ultraviolet curable epoxy resin derived from the epoxidation of an alkyd comprised of: (a) an unsaturated fatty acid, (b) an anhydride or diacid containing cycloaliphatic unsaturation, and (c) a polyol. 2. A resin in accordance with claim 1 , where the unsaturated fatty acid is a tall oil fatty acid which does not contain dimethoxystilbene. 3. A resin in accordance with claim 1 , where the unsaturated fatty acid is a tall oil fatty acid and dimethoxystilbene is subsequently distilled from the alkyd with a wiped film evaporator. 4. A resin in accordance with claim 1 , where the unsaturated fatty acid is oleic acid. 5. A resin in accordance with claim 1 , where the anhydride is 1 ,2,3,6 - tetrahydrophthalic anhydride. 6. A resin in accordance with claim 1 , where the anhydride is methyl tetrahydrophthalic anhydride. 7. A resin in accordance with claim 1 , where the polyol is glycerine. 8. A resin in accordance with claim 1 , where the polyol is trimethylolpro¬ pane. 9. An alkyd comprised of: (a) an unsaturated fatty acid, (b) an anhydride or diacid containing cycloaliphatic unsaturation, and (c) a polyol. 10. A resin in accordance with claim 9, where the unsaturated fatty acid is a tall oil fatty acid which does not contain dimethoxystilbene. 1 1 . A resin in accordance with claim 9, where the unsaturated fatty acid is a tall oil fatty acid and dimethoxystilbene is subsequently distilled from the alkyd with a wiped film evaporator. 12. A resin in accordance with claim 9, where the unsaturated fatty acid is oleic acid. 13. A resin in accordance with claim 9, where the anhydride is 1 ,2,3,6 - tetrahydrophthalic anhydride. 14. A resin in accordance with claim 9, where the anhydride is methyl tetrahydrophthalic anhydride. 15. A resin in accordance with claim 9, where the polyol is glycerine. 16. A resin in accordance with claim 9, where the polyol is trimethylolpro¬ pane. 17. A process for the production of an internally plasticized, ultraviolet curable epoxidized alkyd resin as claimed in claim 1 comprising the steps of: (a) mixing together (1 ) said unsaturated fatty acid; (2) said anhydride or diacid containing cycloaliphatic unsaturation; and (3) said polyol to form a mixture in a vat; (b) heating said mixture rapidly to approximately 100°C, then gradually to 220 °C; (c) holding said mixture at approximately 220 °C for eight hours to sixteen hours; (d) vacuum drying said mixture for 5 to 10 minutes; (e) cooling said mixture; (f) passing said mixture through a wiped film evaporator at 210°C to form a desired alkyd product; (g) mixing the alkyd product with CH 2 CI 2 in a nitrogen environment to form a first solution; (h) cooling said solution with agitation; (i) adding an aqueous sodium acetate and peracetic acid solution to said first solution to form a mixture; (j) allowing the mixture to exotherm to 30°C, then maintaining the temperature at 25-30 °C with agitation; (k) pouring the mixture into distilled water and separating an organic layer; (I) extracting said water with CH 2 CI 2 to form an extract; (m) combining said extract with said organic layer; (n) washing said organic layer with water and sodium carbonate; (o) drying the organic phase with sodium sulfate; and (p) removing CH 2 CI 2 with a roto-evaporator. 18. A process as claimed in claim 17, wherein said nitrogen sweep of said vat is conducted prior to initial heating of said mixture.

Inventors: JONES RAYMOND H, JONES, RAYMOND, H.
Applicants: ARIZONA CHEM, ARIZONA CHEMICAL COMPANY
Application year: 1996
Main classification: C08G63
IPC codes: C08F2, C08G59, C08G63