BRPI0621176A2 - process for preparing a monomer composition acylate (alpha), reactive unsaturated, acylate (alpha), reactive unsaturated, uv curable composition, coating composition, uv curable ink or adhesive composition, and uv curable coating, adhesive composition or ink - Google Patents

Abstract

PROCESS FOR PREPARING A COMPOSITION OF MONOMETER ACYLATE <244>, <225> REACTIVE UNSATURATED, ACYLATE <244>, <225> REACTIVE UNSATURATED, UV CURABLE COMPOSITION, COATING COMPOSITION, ADHESIVE COMPOSITION OR COATABLE PAINTING, UV CURING COATING, UV CURING COATING, UV CURING COATING, UV CURING COATING, UV CURING COATING, UV CURTABLE COVERING, CURING COATING, UV COATED COATING, UV COATED COATING, UV COATED COATING, UV COATED COATING, UV COATED COATING, UV COATED PAINTING UV CURABLE ADHESIVE OR INK. The present invention relates to new (meth) acrylate compositions, their preparation and their use in applications curable by ultraviolet light such as coatings, paints and adhesives.

Description

"PROCESS TO PREPARE AN ACYLATE MONOMER COMPOSITION α, β REACTIVE UNSATURATED, ACILLATE A, β REACTIVE UNSATURED, UV CURABLE COMPOSITION, ADHESIVE UV-CURING, ADHESIVE OR UV-CURING COMPOSITION" .

Generally the present invention relates to novel reactive (meth) acrylate monomer compositions and processes used to prepare such compositions. More particularly, the present invention relates to such reactive monomer compositions which are derived from renewable sources of raw material such as unsaturated vegetable or seed oils. Even more particularly, the present invention relates to such reactive monomer compositions containing at least one amide moiety, ester moiety or triglyceride moiety. The present invention also relates to the use of such reactive monomer compositions for preparing coatings, particularly curable coatings and especially ultraviolet (UV) curable coatings. Reactive monomer compositions may also be used to prepare adhesive compositions or sealant compositions.

Conventional acrylate compositions or resins such as epoxy acrylate resins show a number of defects when used in UV curable coating applications. The resulting UV-cured coatings tend to be brittle rather than flexible and lack proper adhesion to coated substrates for most, if not all, desired applications. Trained technicians understand that impact testing, such as the one detailed below, provides an indication of flexibility and coating adhesion. More particularly, the lack of coating delamination after impact testing indicates at least minimum acceptable adhesion. If examination of a coating or film after impact testing reveals few, if any, visible fractures, trained technicians view the coating or film as having at least minimum acceptable flexibility. In addition, conventional acrylate resins, especially epoxy acrylate resins, have an undiluted viscosity in excess of 4.0 Pascal.sec (Pa.s) (4,000 centipoise (cps)). In order to use such resins, for example, in UV curable coatings, a diluent such as tri (propylene glycol diacrylate) should be added to reduce the viscosity of the coating composition to a practical coating viscosity at room temperature (nominally 25 ° C) of no more than 4.0 Pa.s (4,000 cps) and preferably no more than 2.5 Pa.s (2500 cps). Those using reactive monomers or reactive monomer compositions, especially those using such monomers or monomer compositions in UV curable compositions, desire reactive monomers that can be used with little or no diluent even when the UV curable composition includes , for example, up to forty weight percent (40 weight%) based on the total coating weight of a solid particulate additive such as a pigment. They also want such compositions to produce a UV cured coating with an improvement in at least one of impact resistance, hardness and scratch resistance over UV cured coatings prepared using conventional acrylate resins such as epoxy acrylate. Other desirable but optional features include coating compositions which, when cured, produce flexible films or coatings, e.g. with improvements in at least one of moisture resistance and stain resistance over films made with the commonly obtainable monomers.

US Patent No. 3,713,864 discloses printing ink compositions comprising an epoxidized soybean oil acrylate, or derivative thereof, conventional dyes (e.g., a pigment such as Lithol Rubine (red), benzidine yellow, blue green, iron blue and carbon black phthalocyanine and a radiation sensitizer (eg acetophenone or benzophenone)). US Patent No. 3,713,864 also discloses a method of printing with such ink compositions which comprises exposing the ink composition to an amount of actinic radiation sufficient to polymerize the polymeric constituents of the ink compositions to an undisplaced state and printed substrates. prepared by such method. US Patent No. 3,713,864 teaches the preparation of epoxidized flaxseed oil or epoxidized soybean oil acrylates in column 2, row 54 through column 3, row 7. Preparation begins by epoxidizing flaxseed oil or soybean oil using a conventional epoxidizing agent such as peracetic acid or hydrogen peroxide. Acrylation of the epoxidized oil occurs via, for example, reaction of the epoxidized oil with acrylic acid at a temperature of 100 ° C in the presence of a polymerization inhibitor such as phenothiazine. U.S. Patent No. 3,713,864 also teaches the reaction of an epichlorohydrin / bisphenol A epoxy resin with acrylic acid or methacrylic acid. U.S. Patent No. 4,243,818 defines "hydroformylation" in column 5, lines 8-12 as the production of aldehydes from unsaturated compounds by reaction with hydrogen and carbon monoxide in the presence of a catalyst. The preferred unsaturated compound, by column 5, lines 36-38, is oleyl alcohol, but linoleyl alcohol or linolenyl alcohol can also be used as the unsaturated compound. In column 9, lines 52-58, U.S. Patent No. 4,243,818 teaches the use of an acid halide such as acryloyl chloride to convert alcohols to their corresponding unsaturated esters (for example an acrylate or methacrylate).

U.S. Patent No. 4,128,600 discloses interpenetrating double cure resin compositions. Curable resin compositions contain a radiation sensitive reactive diluent, a saturated polyol and an isocyanate. Exposure of the composition to radiation effects the curing of the reactive diluent.

Subsequent thermal cure forms urethane bonds. According to column 3, lines 38-44, the reactive diluent may be a polymethacrylate or polyacrylate completely substituted with a polyfunctional alcohol. In column 5, lines 10-13, U.S. Patent No. 4,128,600 explicitly states that the reactive diluent should not contain hydroxyl, amine, carboxyl, primary and secondary amides or isocyanate functional groups. Polyfunctional alcohols include, in column 5, lines 43-46, normal and isomeric forms of nonyl, decyl, undecyl, dodecyl, tridecyl and tetradecyl alcohols. In column 18, lines 43-45, U.S. Patent No. 4,128,600 defines pencil hardness testing as an indication of "scratch resistance of resin coating with 9H being the hardest and 6B being the softest".

US Patent No. 4,626,582 discusses acryloxymethyl substituted fatty compounds represented by the formula CH3 - (CH2) m - ((Y) -C- (Z)) - (CH2) nX where m and η are integers, η is greater than 3 the sum of m and η ranges from 7 to 19; Y is hydrogen, methylol or acryloxymethyl group; and one of X and Z is acryloxymethyl and the other is selected from (a) -CN, (b) -C (O) -NR 1 R 2, (c) -C (O) -OR 3, or (d) -CH 2 -NR 4 R 5 wherein R1, R2, R3 are independently lower alkyl that R1 and R2 together may constitute a bivalent hydrocarbon having 4, 5 or 6 aliphatic carbons or 3, 4 or 5 aliphatic carbon atoms and a group or heteroatom; R4 is lower acyl; and R5 is hydrogen or lower alkyl; provided that when X is acryloxymethyl, Y will be hydrogen. By column 2, lines 9-14, such compounds may be used in the preparation of curable coatings.

Column 4, lines 16-31 present teachings regarding radiation curing of such coatings. US Patent No. 5,312,889 discloses in column 1, lines 23-28 that "hydroxy fatty acids in natural oils and fats and their derivatives, or hydroxy fatty acids or amino fatty acids which may be produced from reactive fatty acids. (e.g. oleic acid, linoleic acid) are particularly suitable for preparing technically useful products, especially polymers and plastics. " According to column 2, lines 52-57, "amino group-containing fatty acid residues ... are obtained from unsaturated fatty acid esters using known chemical methods, for example by the double bond addition of a hydrogen halide. such as hydrobromic acid and subsequent nucleophilic substitution of ammonia for halide ".

As stated in column 1, lines 12-21, US Patent No. 6,174,948 relates to novel emulsion or latex compositions containing either vinyl ether, vinyl ester or acrylic ester of a long chain olefin monomer derived from semi-oils. dry or non-dry, a process for producing them, and the utility of such compositions in coatings, adhesives, and inks that do not have essentially any volatile organic components (VOCs) and improved application characteristics and performance properties. In column 5, lines 5-9 illustrative examples of semi-drying oils include safflower oil, sunflower seed oil, soybean oil, and tobacco seed oil, and illustrative examples of non-drying oils include cottonseed oil , coconut oil, rapeseed oil, castor oil, and lesquerella oil. In column 16, lines 36-43, US Patent No. 6,174,948 teaches that preferred starting materials include substituted or unsubstituted fatty acid vinyl esters, fatty alcohol vinyl ethers, and fatty alcohol acrylates and acrylamides or fatty amines. Representative examples of such starting materials without limitation include oleic acid vinyl ester, oleyl acrylate, oleyl methacrylate, oleyl acrylamide, oleyl methacrylamide, and vinyl oleyl ether. Example 1 of U.S. Patent No. 6,174,948 reacts methacryloyl chloride and oleyl alcohol in the presence of triethylamine to produce oleyl methacrylate. Example 2 of U.S. Patent No. 6,174,948 reproduces Example 1, but replaces acryloyl chloride with methacryloyl chloride. Example 8 of U.S. Patent No. 6,174,948 uses the oleyl acrylate of Example 2 in the UV curable formulation.

U.S. Patent No. 6,245,829 discusses radiation curable compositions comprising a mono or multivalent carboxylic ester of a β-hydroxyalkylamide group-containing compound in which the carboxylic ester is derived from an ethylenically unsaturated α, β carboxylic acid. Such a composition may be prepared by reacting a β-hydroxyalkylamide with an unsaturated carboxylic acid chloride, anhydride or ester according to column 2, lines 47-50. Column 3, lines 42-48 notes that after curing coatings prepared with such compositions have many desired properties such as, for example, good chemical properties (resistance to solvents, acids, bases and moisture), good optical properties and appearance, good mechanical properties (such as hardness, flexibility, adhesion, abrasion resistance, strength and durability), good thermal stability and good weatherability.

As used from beginning to end of this report, the definitions given in this paragraph, in subsequent paragraphs, or elsewhere in the report, have meanings ascribed to them wherever they are first defined. Accordingly, "alkyl" means a portion of a mono- or multivalent saturated straight chain or branched aliphatic hydrocarbon having from one to 60 carbon atoms (C1 to C60).

"Alkenyl" means an unsaturated, mono- or multi-chain branched or unsaturated moiety which contains at least one double bond and has from 2 to 60 carbon atoms (C 2 to C 60).

"(Met) acrylate" is a collective term for unsaturated α, β acrylates which includes acrylic acid esters (alkyl acrylate resins) where acryloyl chloride is used as an acylating agent and methacrylic acid esters (methacrylate resins). alkyl) where methacryloyl chloride is used as an acylating agent. "Fatty acid" means a predominantly aliphatic acid of more than 8 carbons.

"Fatty acid ester" means a predominantly aliphatic ester of more than 8 carbons. When setting ranges here, such as in a range of 2 to 10, both ends of the range (e.g. 2 and 10) fall within the range boundaries unless specifically excluded otherwise.

A first aspect of the present invention is a reactive monomer composition comprising a poly (acrylate, unsaturated) amide represented by Formula I:

<formula> formula see original document page 8 </formula>

Formula I

wherein R1 is a polyvalent alkenyl moiety; R2 is hydrogen or a monovalent alkyl moiety; R3 is nothing or a polyvalent alkenyl moiety; R4 is polyvalent alkenyl moiety; R5 is H, a monovalent alkyl moiety or a moiety represented by Formula II: <formula> formula see original document page 9 </formula>

Formula II

wherein R4 is as defined above and R7, R8 and R9 are independently hydrogen or a monovalent alkyl moiety; R6 is a parcel having Formula III:

<formula> formula see original document page 9 </formula>

Formula III

wherein R7, R8 and R9 are independently defined as above, in, η and o are independently 0 or 1, however, as long as the sum of m, η and o is a positive integer greater than zero (for example, 1 ).

A second aspect of the present invention is a process for preparing the reactive monomer of the first aspect. The process comprises sequential steps: (a) reacting an alkanolamine with a compound having at least one reactive hydroxy moiety or group, the compound being selected from the group consisting of unsaturated, modified or unmodified vegetable oils, fatty acids and fatty acid esters, to convert the compound to an amide polyol; and (b) reacting the amide polyol with an unsaturated α, β acylating agent to convert the amide polyol to a poly (α, unsaturated) amide polyacrylate.

A third aspect of the present invention is a reactive monomer composition comprising a poly (α, unsaturated) acrylate represented or by Formula IV: <formula> formula see original document page 10 </formula>

Formula IV

or by Formula V:

<formula> formula see original document page 10 </formula>

Formula V

wherein R1 is as defined above; R10 is a portion of the following formula:

<formula> formula see original document page 10 </formula>

wherein R7, R8 and R9 are as defined above; R11 is hydrogen or a hydrocarbyl moiety; η and ρ are O or a positive integer within the range 1-20; a, b, c, d, e, f, g, h, i, j, k and 1 are independently 0 or 1, however, as long as at least one of a sum of a, b, c, d, e, f , g, hei or a sum of j, k and 1 is a positive integer greater than zero (for example, 1); and X is:

<formula> formula see original document page 10 </formula> wherein R10 is as defined above, R12 and R13 are independently hydrogen or a hydrocarbyl moiety. A fourth aspect of the present invention is a process for preparing the reactive poly (acrylate α, β unsaturated) of the third aspect. The process comprises sequential steps: (a) reacting an epoxy functionalized vegetable oil, an epoxidized fatty acid or a water epoxidized fatty acid ester, a carboxylic acid or an alcohol in the presence of an acid catalyst to form a polyol; and (b) reacting the polyol of step (a) with an unsaturated α, β acylating agent to form a reactive monomer composition comprising an unsaturated poly (acrylate, α, β).

A fifth aspect of the present invention is a process for preparing a reactive unsaturated α, β acrylate monomer composition, the process comprising sequential steps: (a) polymerizing at least one fatty acid or fatty acid ester, the fatty acid or acid ester fatty acid containing at least one reactive hydroxy moiety with a polyol initiator to form a hydroxy functionalized aliphatic polyester; (b) reacting the polyester of step (a) with an unsaturated acylating agent α, β to form a reactive α, β unsaturated acrylate.

A sixth aspect of the present invention is a reactive α, β unsaturated acrylate prepared according to the process of the fifth aspect.

A seventh aspect of the invention is a UV curable composition comprising the reactive monomer composition of the first aspect or the reactive acrylate of the third or sixth aspect of the invention.

An eighth aspect of the invention is a UV curable coating, adhesive composition or ink composition comprising the UV curable composition of the seventh aspect.

A ninth aspect of the present invention is a coating composition, adhesive composition or UV cured paint prepared from the corresponding composition of the eighth aspect.

The reactive monomer composition of the first aspect comprises or includes a poly (α, β unsaturated) amide represented by Formula I:

Formula I

is a polyvalent alkenyl moiety; R2 is hydrogen or a monovalent alkyl moiety; R3 is nothing or a polyvalent alkenyl moiety; R4 is polyvalent alkenyl moiety; R5 is H, a monovalent alkyl moiety or a moiety represented by Formula II:

<formula> formula see original document page 12 </formula>

Formula II

wherein R4 is as defined above and R7, R8 and R9 are independently hydrogen or a monovalent alkyl moiety; R6 is a parcel having Formula III:

<formula> formula see original document page 12 </formula>

Formula III

wherein R 7, R 8 and R 9 are independently defined as above, in, n and o are independently 0 or 1, provided that the sum of m, n and o is a positive integer greater than zero (for example, 1, 2 or 3). In a preferred variation of the amide, R 1 is a bivalent alkenyl or alkyl moiety of 1-20 carbons; R2 is hydrogen or an alkyl moiety containing from 1 to 20 carbons; R3 is nothing or methylene; R4 is ethylene or propylene; R5 is hydrogen, methyl or a moiety represented by Formula II wherein R4 is ethylene, R7 is hydrogen or methyl and R8 and R9 are hydrogen; and R 6 is a moiety represented by Formula III wherein R 7 is hydrogen or methyl and R 8 and R 9 are hydrogen. Specific examples of (meth) acrylate substituted amides include methyl 11-hydroxy undecanoate amide acrylate, 12-hydroxy stearate amide acrylate, methyl 12-hydroxy stearate amide acrylate and ricinolamide acrylate.

The preparation of poly (α, β unsaturated) amide amide comprises at least two sequential steps (a) and (b).

Step (a) comprises reacting an alkanolamine with a compound having at least one reactive hydroxy moiety, the compound being selected from the group consisting of modified or unmodified vegetable oils, fatty acids or fatty acid esters to convert the compound to a polyol amide. Step (b) comprises reacting the amide polyol with an unsaturated α, β acylating agent to convert the amide polyol to a poly (α, unsaturated) amide polyacrylate.

In step (a), alkanolamine and the compound are present in a molar ratio of alkanolamine to compound falling within the range of 4: 1 to 1: 1. Preferably, the range is from 3: 1 to 1: 1, more preferably from 2: 1 to 1: 2, and even more preferably from 2: 1 to 1.5: 1.

Step (a) is an endothermic reaction which requires heating the reactants to a temperature of at least 60 ° C, preferably at least 80 ° C, even more preferably at least 100 ° C. Preferably the temperature is not higher than 150 ° C, more preferably not higher than 130 ° C and even more preferably not higher than 120 ° C.

Preferably, step (a) includes the use of a nonreactive solvent for the reagents. The solvent is used in an amount sufficient to place solid reactants in solution at the temperature specified above.

Preferably, the solvent is selected from toluene, chloroform and ethyl ether, most preferably toluene.

Preferably, step (a) includes the use of a catalyst such as potassium hydroxide. More preferably, a 30% solution of potassium hydroxide in methanol. Although the use of methanol is optional, it is also preferred because it aids in catalyst dissolution. Other catalysts that may be used include sodium hydroxide and sodium methoxide. Preferably, the catalyst is used within the range of 0 part weight (bpw) to 5 bpw per 100 bp diethanolamine.

Recovery of the polyol amide produced in step (a) occurs by standard procedures such as those detailed in the examples provided below. Such procedures include washing with an aqueous saline solution such as a 2% by weight solution of sodium chloride in water, the percentage by weight based on the total weight of solution, drying with anhydrous magnesium sulfate and rotary evaporation to remove. toluene. In step (b), the polyol amide and α, β unsaturated acylating agent are present at a molar ratio of polyol amide to α, β unsaturated acylating agent that falls within the range of 1: 1 to 0.2 :1. Preferably the display is from 0.75: 1 to 0.2: 1, more preferably from 0.5: 1 to 0.2: 1, and even more preferably from 0.4: 1 to 0.2: 1.

Like step (a), step (b) preferably includes the use of a nonreactive solvent for reagents. The solvents specified for step (a) also work for step (b).

Step (b) is an exothermic reaction which requires cooling the reagents to a temperature no higher than 30 ° C, preferably no higher than 20 ° C, even more preferably no higher than 10 ° C. Preferably, the temperature is at least 0 ° C, and more preferably at least 5 ° C. At temperatures below 0 ° C (e.g. -5 ° C), the reactants tend to solidify, thereby interfering with further processing.

Recovery of the poly (acylate α, unsaturated) amide produced in step (b) occurs by standard procedures such as those detailed in the examples provided below, especially Example 2.

When using a compound other than castor oil or a castor oil derivative, the preparation of the (α, β unsaturated acylate) amide preferably includes a precursor step preceding step (a) and comprising at least partially reducing hydroformylation. a starting material selected from the group consisting of unsaturated vegetable oils, fatty acids and fatty acid esters.

U.S. Patent No. 4,243,818, the teachings of which are incorporated herein by reference, teaches hydroformylation.

When used, the precursor step preceding step (a) includes sufficient hydroformylation to functionalize or react with more than zero percent unsaturation in the starting material up to 100 percent of such unsaturation.

Preferably, the hydroformylation is sufficient to react with at least (>) 20 percent (%) unsaturation, more preferably> 50% unsaturation and most preferably> 80% unsaturation.

Additional references, the teachings of which are incorporated herein by reference to the maximum extent permitted by law, which discuss hydroformylation include: US Patent No. 4,423,162 (especially Example 34), US Patent No. 4,723,047, Canadian Patent Application (CA ) 2,162,083, WO 2004/096744, US Patent No. 4,496,487, US Patent No. 4,216,344, US Patent No. 4,304,945 and US Patent No. 4,229,562.

The teachings of U.S. Patent No. 4,423,162, especially those found in column 3, line 50 to column 4, line 36, are particularly instructive for those seeking to practice reducing hydroformylation. In that part, a prepared hydroxy ester monomer starting material is prepared by hydrogenating a hydroformylated unsaturated carboxylic acid ester or ester. Appropriate unsaturated acids can be obtained by dividing a triglyceride into its respective component fatty acids. US Patent No. 4,423,162 notes that fatty acid sources include fatty oils such as tallow and most plant sources including soybean oil, sesame, sunflower, tallow and the like, but starting fatty acids are preferred. which are in the form of a methyl ester. US Patent No. 4,423,162 teaches that the introduction of a hydroxymethyl group can be readily accomplished by a hydroformylation process using cobalt or rhodium catalysts, followed by hydrogenation of the formyl group to obtain the hydroxymethyl group by catalytic methods or by chemical reduction. . Accordingly, U.S. Patent No. 4,423,162 also refers to and incorporates by reference the procedures described in detail in U.S. Patent Nos. 4,216,343, 4,216,344, 4,304,945, and 4,229,562.

Preferred unsaturated α, β acylating agents include acid halides. Especially preferred unsaturated α, β acylating agents include acryloyl chloride when preparing compositions containing acrylate or methacryloyl chloride when preparing compositions containing methacrylate. If a mixture of acrylate plots and methacrylate plots is desired, a mixture of acryloyl chloride and methacryloyl chloride may be used.

When the compound reacting with an alkanolamine in step (a) is derived from an unsaturated vegetable oil, the compound is preferably a hydroxy functional vegetable oil, the unsaturated vegetable oil being selected from the group consisting of safflower oil, sunflower seed oil , linseed oil, peanut oil, olive oil, tobacco seed oil, cottonseed oil, coconut oil, rapeseed oil, canola oil, corn oil, lesquerella oil or a modified version of any one of these oils. Modifications of such oils include reducing hydroformylation. When the compound reacting with an alkanolamine in step (a) is derived from a fatty acid, the compound is preferably a hydroxy functional acid, the acid being selected from oleic acid, linoleic acid, and linolenic acid.

When the alkanolamine-reacting compound in step (a) is derived from a fatty acid ester, the compound is preferably a hydroxy-functional ester, more preferably a hydroxy-functional fatty acid methyl ester, especially a fatty acid methyl ester. hydroxy functional in which the methyl ester is selected from the group consisting of methyl oleate, methyl 10-undecenoate, methyl 9-decenoate, methyl linolenate, and methyl linoleate. Preferred starting materials include hydroxymethyl fatty acids, hydroxymethyl fatty acid esters, castor oil and castor oil derivatives. Especially preferred starting materials include those selected from the group consisting of hydroxymethyl stearate, hydroxymethyl methyl stearate, ricinoleic acid and ricinoleic acid esters.

The reactive monomer composition of the third aspect comprises a poly (α, unsaturated β-acylate) represented or by Formula IV: <formula> formula see original document page 18 </formula>

Formula IV

or by Formula V:

<formula> formula see original document page 18 </formula>

Formula V wherein R1 is as defined above, portion of the following formula:

<formula> formula see original document page 18 </formula>

wherein R77 R8 and R9 are as defined above; R11 is hydrogen or a hydrocarbyl moiety; η and ρ are O or a positive integer within the range 1-20; a, b, c, d, e, f, g, h, i, j, k and 1 are independently 0 or 1, however, as long as at least one of a sum of a, b, c, d, e, f , g, hei or a sum of j, k and 1 is a positive integer greater than zero (e.g., 1, 2, 3, 4 or 5); eXé: <formula> formula see original document page 19 </formula>

wherein R10 is as defined above, R12 and R13 are independently hydrogen or a hydrocarbyl moiety. Preferably, the poly (unsaturated α, β-acylate) of the third aspect is prepared by a process comprising sequential steps (a) and (b). Step (a) comprises reacting at least a first reagent selected from an epoxy functional vegetable oil, an epoxidized fatty acid or an epoxidized fatty acid ester with at least a second reagent selected from water, a carboxylic acid or an alcohol in the presence of of an acid catalyst to form a polyol. Sequential step (b) comprises reacting the polyol of step (a) with an unsaturated α, β acylating agent to form a reactive monomer composition comprising a poly (α, β unsaturated) acylate. Preferably, the unsaturated α, β acylating agent is selected from those disclosed above.

Preferred epoxy functional vegetable oils suitable for use as a first reagent include vernonia oil, epoxidized soybean oil, or epoxidized flaxseed oil.

Preferred epoxidized fatty acids suitable for use as a first reagent include epoxidized undecenoic acid, and epoxidized oleic acid.

Preferred epoxidized fatty acid esters suitable for use as a first reagent include epoxidized methyl oleate, epoxidized methyl 10-undecenoate and epoxidized methyl 9-decenoate.

Preferred carboxylic acids suitable for use as a second reagent include acetic acid and formic acid.

Preferred suitable alcohols for use as a second reagent include methanol, ethanol, propanol and butanol. Preferred acid catalysts include ion exchange references, preferably a cation exchange resin such as DOWEX ™ MSC-I cation exchange resin (The Dow Chemical Company) and mineral acids (e.g. sulfuric acid).

Step (a) effectively opens epoxy ring structures present in the first reagent (for example an epoxidized or epoxy functional vegetable oil) and produces a polyol. Step (a) includes heating with stirring, and preferably in an inert gaseous atmosphere (e.g. nitrogen), a combination of the first reagent, the second reagent and an acid catalyst. Step (a) is an endothermic reaction which requires heating the reactants to a setpoint temperature of at least 25 ° C, preferably at least 50 ° C, even more preferably at least 65 ° C. Preferably the temperature is not higher than 150 ° C, more preferably not higher than 120 ° C and even more preferably not higher than 100 ° C. An alternative to nitrogen is to be able to use another inert gas such as helium, or a mixture of inert gases.

Recovery of the first open ring reagent in step (a) occurs by standard procedures such as those detailed in the examples provided below, especially Example 6. Nitrogen sweep vacuum filtration followed by vacuum distillation provides very satisfactory results.

Sequential step (b) comprises reacting the polyol of step (a) with an unsaturated α, β acylating agent to form a reactive monomer composition comprising a poly (α, β unsaturated) acylate. Step (b) largely reproduces step (b) detailed above except for replacing the polyol produced in step (a) with the amide polyol produced in step (a). Example 7 below illustrates step (b) and details the recovery of poly (acylate α, unsaturated). The process of the fifth aspect of the present invention produces the α, β unsaturated acylate monomer composition of the sixth aspect. The process comprises sequential steps (a) and (b). Step (a) comprises polymerizing at least one first reagent containing at least one reactive hydroxy moiety, the first reagent being a fatty acid or fatty acid ester, with a polyol initiator to form a hydroxy functional aliphatic polyester. Sequential step (b) comprises reacting the hydroxy-functional aliphatic polyester from step (a) with an unsaturated α, β acylating agent to form a reactive unsaturated α, β acylate. Preferably, the unsaturated α, β acylating agent is selected from those disclosed above.

Polymerization of a first reagent with a polyol initiator preferably occurs at a temperature within the range of 168 ° C to 230 ° C, more preferably within the range of 190 ° C to 200 ° C. Preferably, polymerization takes place under an inert gas layer (also referred to as in the presence of an inert gas medium) in order to minimize color formation.

The reaction which occurs in step (b) preferably takes place in an inert gaseous atmosphere (e.g. nitrogen) at a temperature within the range of 0 ° C to 30 ° C, more preferably within the range of 5 ° C to 20 ° C, and most preferably within the range of 5 ° C to 10 ° C. When rotary evaporation is used to remove a solvent (eg toluene) as part of product recovery, limiting the temperature during rotary evaporation to a maximum of 60 ° C produces satisfactory results.

The first reagent may be prepared by at least partial hydroformylation, which is defined above, provided that a minimum level of partial hydroformylation for the fifth aspect is 80% unsaturation present in the first reagent prior to hydroformylation. Preferred fatty acids suitable for use as a first reagent in the process of the fifth aspect include 12- (hydroxymethyl) stearic acid, (hydroxymethyl) stearic acid diol and (hydroxymethyl) stearic acid triol.

Preferred fatty acid esters suitable for use as a first reagent in the process of the fifth aspect include 12- (hydroxymethyl) stearate, (hydroxymethyl) stearate diol and (hydroxymethyl) stearate triol. Preferred polyol initiators include glycerol, glycerol ethoxylate, poly (ethylene glycol), and poly (propylene glycol).

The poly (acylate α, unsaturated) amide and α, β unsaturated acylate monomer compositions disclosed above have practical utility as a UV curable component of UV curable compositions such as UV curable paint compositions and UV curable adhesive compositions. UV curable coating compositions. Such compositions, subsequent to exposure to UV curing conditions sufficient to cure the compositions, produce commercially desirable results in terms of cured inks, cured adhesives and cured coatings respectively.

The compositions of the present invention may include one or more non-reactive components conventionally added to the UV curable coating compositions. Such non-reactive components include, without limitation, pigments, fillers, stabilizers and solvents.

In preparing an ink based on the reactive monomers of the present invention, any conventional pigment or coloring agent known in the art may be used. For example, various organic and inorganic pigments may be widely used as coloring agents, but non-toxic anti-corrosive pigments are preferred. Examples of such pigments include phosphate-type anticorrosive pigments such as zinc phosphate, calcium phosphate, aluminum phosphate, titanium phosphate, silicon phosphate, orthophosphates and fused phosphates thereof; anti-corrosion type molybdate pigments such as zinc molybdate, calcium molybdate, calcium and zinc molybdate, potassium zinc molybdate, potassium zinc phosphomolybdate and calcium potassium phosphomolybdate; and borate anti-corrosion pigments such as calcium borate, zinc borate, barium borate, barium metaborate and calcium metaborate. Selection of an appropriate amount of coloring agent or pigment depends on whether a given end-use application for reactive monomers of the present invention requires or lends itself coloration from pigments or coloring agents. For radiation curable printing inks, pigment loads as high as 40 percent by weight based on the total weight of such inks produce satisfactory results. For end-use applications requiring a colorless product, pigment or coloring agent may be omitted.

Analytical Procedures

The analytical procedures used for 1H NMR, 13C NMR, FTIR are based on standard methods as described in an ACS professional reference book entitled "Spectroscopy of Polymers" by Jack L. Koening. Other test methods used herein are described below.

% Hydroxy is determined via titration according to test method ASTM D 4274.

Coating thickness

A Fisher Multiscope thickness analyzer is used to determine the thickness of non-magnetic coatings deposited on ferromagnetic substrates. Fisher Multiscope includes a probe and operates via magnetic induction to indicate coating thickness after placing the probe against the coating and activating Fisher Multiscope. The coating thickness values reported herein represent an average of 15 coating thickness measurements.

Methyl Ethyl Ketone (MEK) Double Frets - Method ASTM D 5402 Pass the smaller end or rounded end of a 4.4 kg ball hammer covered with 8 layers of gauze and MEK back and forth over the surface. a coated panel until the coating fails. Use only the weight of the hammer and the force required to guide the gauze-covered end through the coating in this test. Coating failure occurs in response to exposure of a panel substrate under the coating. Use copper acid sulfate to verify substrate exposure and coating failure. Repeat the test twice, determine the arithmetic mean of such a test and record that average as "MEK double friction failure number in the coating".

Pencil Test Film Hardness - ASTM D 3363 Method

Lay a paneled panel on a firm horizontal surface. Have an operator hold a pencil of known hardness firmly against the coating or film at a 45 ° angle and push the pencil towards the operator's body in a 6.5 mm stroke. Begin this test with the softer graphite pencil (6B) and continue testing with progressively harder graphite pencils (toward 9H) until the stroke causes the pencil to cut or groove in the coating or film. Report the hardness of the hard pencil by the hardness of the graphite immediately preceding that pencil that cuts or grooves the pencil. Nail Scratch Test

In this subjective test, an operator attempts to nail the coating surface using moderate pressure and then examines the surface for visual damage such as mutilation. Resistance of Organic Coatings to the Effects of Rapid Deformation (Impact) - Method ASTM D 2794 Drop a standard weight of 8.8 kg at a distance over a penetrator that deforms both cured film and substrate as well as the panel or substrate underlying the coating. or cured film. The penetrator may be placed either against the cured film to intrude and assess the direct impact or against the panel or substrate surface opposite to that on which the cured coating is bonded to impose an extrusion force to assess resistance to reverse impact. . Gradually increase the weight drop distance to a distance where coating failure occurs. Cured coatings or films generally fail by cracking, which becomes more visually evident when viewed through an enlarger, especially after an acidic solution of copper sulphate is applied to the cured coating or film after deformation.

The following examples illustrate, but do not limit, the present invention. All parts and percentages are based on weight unless stated otherwise. All temperatures are in ° C. Examples (Ex) of the present invention are designated by arabic numbers and Comparative Examples (Ex Comp) are designated by capital letters of the alphabet. Unless otherwise stated herein, "ambient temperature" and "ambient air temperature" are nominally 25 ° C.

Ex 1 - Preparation of a diethanolamine amide triol and methyl 11-hydroxy undecanoate

Methyl 10-undecenoate (commercially obtainable from Aldrich) is subjected to reducing hydroformylation to prepare methyl 11-hydroxy undecanoate using procedures incorporated hereinbefore by reference, especially US Patent No. 4,496,487 in column 4, rows 9 -19.

Add 158.4 g (0.7322 mol) of methyl 11-hydroxy undecanoate, 154.8 g (1.472 mol) of diethanolamine, 2.6 g (0.39 mol) of 85% by weight hydroxide solution. of potassium (in methanol) and 140 mL of toluene in a 500 mL round bottom flask equipped with a magnetic stir bar and a water cooled reflux condenser. Place the balloon in a sand bath on an electric heating blanket. Control the sand bath temperature using a temperature controller connected to a thermocouple immersed in the sand bath. With the sand bath heat the flask contents to 60 ° C with stirring whereby the solid components of the flask contents dissolve in toluene to produce a clear colorless solution.

Maintain the solution temperature at 60 ° C with continuous agitation for 24 hours before taking a sample from the solution and subjecting it to Fourier conversion infrared analysis. Analysis shows a trace amount of ester absorbance indicated by a small peak at 1729 cm -1.

Add another 10.2 g (0.1 mol) of diethanolamine and keep the temperature at 60 ° C with continuous stirring for 18 hours before allowing the flask contents to cool to room temperature. Subject the contents of the flask to rotary evaporation at a temperature of 35 ° C and a vacuum of 15 kPa for two hours to remove methanol produced during the reaction of the flask contents, thereby leaving a solid reaction product.

Add 350 ml of a 2% by weight aqueous solution of sodium chloride (NaCl) to the flask and stir the contents (solid reaction product and aqueous NaCl solution) for three hours. Vacuum filter the contents of the flask through a raw glass frit Büchner funnel. Rinse the solid contents of the funnel with 100 mL of 2% aqueous NaCl solution and then repeat stirring of the solid contents with 350 mL of 2% aqueous NaCl solution for 3 hours. Repeat filtration through the Büchner funnel and then rinse the funnel solid contents first with two 100 mL aliquots of fresh 2% NaCl aqueous solution and then with two 100 mL aliquots of deionized water.

Allow air drying of solid contents in a smoke suction dome for three days. The dry solid contents have a weight of 180.7 g. Place the dry solid contents and 500 ml of toluene in a mixing vessel and mix for two hours. Vacuum filter the contents of the mixing vessel through a raw glass frit Büchner funnel, then rinse the solid contents of the funnel with two 200 mL aliquots of toluene before air drying the solid contents overnight. . Subject the dried solid contents to rotary evaporation until the white powder contents show a constant weight. Constant weight, 158.9 g, represents a 75% yield of theory.

White powder analysis by FTIR, hydrogen nuclear magnetic resonance (1H NMR) spectroscopy, and carbon 13 nuclear magnetic resonance spectroscopy (13C NMR) support a structure shown in formula VI below.

<formula> formula see original document page 27 </formula>

Formula VI Experimental Amide Triol Ex 2 - Acylation of Ex 1 Amide Triol Place 41.6 g (0.144 mol; 0.431 hydroxy equivalent (OH)) of Ex 1 Amide Triol and 200 mL of toluene in a round bottom flask. 1 liter equipped with a mechanical stirrer and a reflux condenser cooled to -5 ° C with a water / ethylene glycol mixture. Cool the contents of the flask to 70 ° C using an ice bath before adding 46.82 g (0.517 mol) of acryloyl chloride and another 50 mL of toluene to the flask. Add dropwise 58.62 g (0.4536 mol) of N, N-diisopropylethylamine to the flask over a period of 15 minutes keeping the ice bath at 7 ° C. Add a second 50 mL aliquot of toluene to the flask, then remove the ice bath and shake the flask contents for 24 hours.

Using a separatory funnel, wash the toluene layer once with 200 mL of 2% aqueous NaCl solution and then twice with 200 mL aliquots of aqueous sodium hydrogen carbonate (sodium bicarbonate) solution (NaHCO3). at 3%. Dry the washed sodium sulfate toluene layer (Na 2 SO 4) and then vacuum filter the washed and dried toluene layer through a medium glass frit Büchner funnel. Add 0.1 g A-methoxyphenol in 5 mL methanol (MeOH) to the filtrate, then rotate the filtrate for 5.5 hours at 40 ° C and 1.2 kPa to yield a toluene free residue. Add 200 mL of anhydrous methanol to the stirring residue and then separate the solids from the liquid filtrate using No. 1 filter paper. Subject the liquid filtrate to rotary evaporation at 40 ° C and 9 mm Hg to remove methanol and produce a product. Transparent liquid end. The final product weighs 66.07 g, which is equivalent to a theoretical yield of 74.0% and has a viscosity at 25 ° C of 0.11 Pa.s (110 cps) measured by an I.C.I. and plate rheometer according to ASTM Procedure D 4287. FTIR and 1H NMR analyzes of the end product support an amide acylate structure shown in Formula VII below.

<formula> formula see original document page 28 </formula>

Formula VII. Experimental Amide Triacylate Ex 3 - Preparation of UV Cured Coatings Using Ex 2 Amide Triacylate

In a glass bottle combine 8.72 g of the Ex 2 amide triacylate with stirring, 0.24 g of a 50/50 mixture of benzophenone and 1-hydroxy-cyclohexyl phenyl ketone (IRGACURE ™ 500 obtainable) Aldrich), 0.2 g methyl diethylamine, two drops of polysiloxanes (BYK ™ 307, commercially available from BYK Chemie, Japan Ltd.), and four drops of a non-silicone defoaming agent (BYK ™ A-555 (commercially available from BYK Chemie, Japan Ltd.) to produce a formulated coating solution having a viscosity of 0.12 Pa.s (120 cps) at 25 ° C.

Using a BYK-Gardner No. 32 lamination section bar, remove or deposit coatings of the formulated coating solution under aluminum panels held in place on a drawing board. The coatings have a thickness of 0.05 mm to 0.08 mm. Cure the coatings by passing the coated panels under a mercury lamp (UV Process Supply Inc. bulb type H bulb, part no. HS6808A4C-410) spaced 7.6 cm above the coated panels at a rate of 5.08 χ 10 "2 m / s. The mercury lamp has an irradiation temperature of 38.30C (1010F).

Determine the glass transition temperature (Tg) of the cured coating via differential scanning calorimetry (DSC) using a programmed heating rate of 10 ° C per minute. Trained technicians recognize Tg of a material as that point on a DSC graph where a clear change in the material heat flow occurs when the material changes from vitreous to rubbery state. Evaluate pencil hardness according to ASTM D 3363 explained above. Tg and coating hardness are 29 ° C and HB, respectively. Ex 3 shows that a representative amide acylate of the present invention produces a curable coating composition with a commercially acceptable operating viscosity less than or equal to 4.0 Pa.s (4,000 cps). Once deposited and cured, the coating has a commercially desirable Tg of more than 25 ° C. HB pencil hardness broadly meets the requirements for many applications, especially for wood coatings where hardness greater than 6B is desired and hardness of 2B or greater is preferred. Trained technicians can quickly determine if an HB hardness is sufficient for your particular end use application. Ex 4 - Preparation of UV-cured coatings from a mixture of an Ex 2 epoxy acrylate and amide triacylate

Repeat Ex 3 with several changes. As a first change, decrease the amount of amide triacylate to 5.168 g, add 7.517 g of an experimental epoxy bisphenol A acrylate (25 Pa viscosity at 19 ° C (19,000 cps), density 1.11 to 1 , 15 g / cm3 and an epoxy acrylate content of 3.6 millimols per gram formerly obtainable from The Dow Chemical Company under the tradename XZ 92554.00) and place the bottle containing the amide triacrylate epoxy acrylate on a vibrator manufactured by Eberbach Corporation under a heating lamp that is spaced 15.2 cm from the bottle and exposes the bottle to a temperature of approximately 500 ° C for a period of 15 minutes to obtain a clear homogeneous mixture. Then add with stirring 0.35 g of the same IRGACURE ™ as Ex 3, 0.30 g of methyl diethylamine, two drops of BYK ™ A-555 and one drop of BYK ™ 307 to produce a formulated coating composition having a viscosity. 0.9 Pa.s (900 cps). Summarize Tg Data and Pencil Hardness on

Table 1 below. A bisphenol A epoxy acrylate material is believed to be comparable to the most recently noted material noted above which is SARTOMER ™ CN104 (Sartomer Company, viscosity at 25 ° C of 18.9 Pa.s (18,900 cps)).

Ex Comp A - Preparation of UV-cured coatings based on a mixture of epoxy acrylate and tri (propylene glycol) diacrylate

Repeat Ex 4 with several changes. First, increase the amount of bisphenol A epoxy acrylate to 22.6 g and replace 15.067 g of tri (propylene glycol) diacrylate (Aldrich Chemical Company) for the amide triacrylate of Ex 2. Second, increase the vibrator time to 20 minutes Third, increase the amounts of IRGACURE ™ 500 and methyl diethylamine, respectively, to 1.02 g and 0.87 g and double the amounts of BYK ™ 307 and 10 BYK ™ 555. Summarize the Tg and pencil hardness data in Table 1. below, down, beneath, underneath, downwards, downhill.

Table 1. Properties of UV-cured coatings

<table> table see original document page 31 </column> </row> <table>

Ex 2 amide, function as satisfactory diluents for an epoxy acrylate in UV curable formulations. At lower cure rates such as 25.4 x 10-3 m / s (25 fpm) or 152.4 x 10-3 m / s (30 fpm), amide acylates also provide improved scratch resistance over same conventional acrylate diluent. If scratch resistance is of little or no importance, such as in paint application, compositions of the present invention with even higher cure rates of 177.8 x 10-3 m / s (35 fpm) or more may be used. . Ex 5 - Preparation of an Ex 2 amide triacrylate-based UV curable paint composition Prepare a pigment concentrate by passing five times a combination of four materials through milling rollers. The materials and amounts, based on concentrate weight, are: 37.15 wt% blue pigment (Phthalic blue 249-3054, Sun Chemical), 37.15 wt Ex 2 amide triacrylate, 15.7% by weight of modified polyester acrylate (FLEXCURE ™ D30, Ashland), and 10.0% by weight of trimethylolpropane triacrylate (SARTOMER SR ™ 351, Sartomer Company).

Prepare a coating paint by manually mixing the following components in a jar: 32.1 parts by weight (bpw) of the pigment concentrate; 45.5 bpw of a patented polyester acrylate (SARTOMER CN ™ 2273, Sartomer Company); 10.3 bpw of the same trimethylolpropane triacrylate as the pigment concentrate; 0.5 bpw of an acrylic polymer flow control additive (RESIFLOW ™ LG-99, Estron Chemical Co.); and 9.2 bpw of phosphine oxide, alpha hydroxy ketone and a benzophenone derivative (SARCURE SR ™ 1135, Sartomer Company). Using a Pamarco manual waterproofing set fitted with a 550 laser-engraved ceramic anilox printing cylinder and having a screen with a volumetric capacity of 4.19 cm3 / m2 to use ink on a variety of substrates and conformation proofs. The substrates are 176 kg Centura Gloss catalog paper laminate sheets (commercially available from Leneta under the tradename 5DX), and polyester film.

The procedure for using the manual waterproofing device is as follows: (a) placing the stock to be printed on a flat, clean and smooth surface; (b) adjust the position of the platen to a desired setting and lock it in this position with small thumbscrews; (c) spill about 2.5 mL of the ink or coating to be tested on top of a tweezer located between the print cylinder and a second stock-contact rubber cylinder; (d) turning the cylinders by hand to completely "paint over" the anilox cylinder; and (e) secure the waterproofer so that the rubber cylinder rests on the stock and drag it toward the operator, using a moderately fast, even stroke, polished with just enough pressure to rotate the cylinders without slippage.

Curing inks by passing the tests through a Hanovia UV-6 conveyor unit equipped with a 300 watt H bulb at a line speed of 1.01 m / s (200 fpm). An ink assessment of the cured evidence shows that the ink is very bright and has a strong blue color with no visually discernible mist.

Ex Comp B - Preparation of a UV Curable Ink Composition Based on Commercially Obtainable Polyester Acrylates

Repeat Ex 6, but replace a patented polyester acrylate (SARTOMER CN ™ 2270, Sartomer Company) with Ex 2 amide triacrylate when preparing pigment concentrate. An ink assessment of cured proofs shows that, compared to Ex 5 cured proofs, Ex Comp B cured ink appears to be less dense and less transparent than Ex 5 cured ink.

Ex 6 - Preparation of an open ring epoxidised soybean oil

Add 250 g of an epoxidized soybean oil (ESO) (plasticizer FLEX0L ™, EPO, 7.0% by weight of epoxide oxygen, approximately 1.09 mol of epoxide commercially available from The Dow Chemical Company) and 250 g ( 7.8 moles of methanol (MeOH) in a 1 liter three neck round bottom flask equipped with a mechanical stirrer and a heating blanket. Fit a condenser topped with a nitrogen / vacuum inlet on the first neck. Insert a thermocouple probe connected to an electronic temperature controller into the second neck. Cap the third neck. Shake the contents of the flask (ESO and MeOH) at a stirring speed of 300 rpm, and simultaneously evacuate the flask and refill it with nitrogen three times to remove air from the container and replace it with a gaseous nitrogen atmosphere. Heat the contents of the flask with continuous agitation at the same rate to a setpoint temperature of 65 ° C. During heating, the counter contents change to a clear light yellow homogeneous solution at a temperature of about 50 ° C.

After the contents of the flask have reached setpoint temperature, add to the flask 388 g of ion exchange resin beads (DOWEX ™ MSC-1, The Dow Chemical Company), previously washed with MeOH and air dried. Increase stirring speed to 50 rpm while maintaining reactor contents at setpoint temperature and continuously stirring at that speed for 18 hours. Stop the shaking and allow the contents of the flask, a homogeneous solution, pale pale yellow and ion exchange resin beads, to cool to room temperature (nominally 25 ° C). Vacuum filter the contents of the flask to separate the (filtered) solution from the ion exchange resin beads. Vacuum distillate the filtrate with a nitrogen sweep using a rotary evaporator with a bath operating at a setpoint temperature of 60 ° C and simultaneously gradually decreasing (over a time period of approximately one hour) the pressure to a value within range limits from 1.3 to 2 kPa (10 to 15 mm Hg). After one hour at setpoint temperature and pressure drop, increase setpoint temperature to 70 ° C and maintain that temperature for two hours with slight vacuum sweeping before shutting off vacuum and heating and allowing distilled filtrate to vacuum cool to ambient pressure and temperature. Analyze the vacuum distilled filtrate, a clear light golden yellow oil, for hydroxy group via titration using ASTM test method D 4274. This method is based on titration again with 1N sodium hydroxide (NaOH) solution after reacting an aliquot of the filtrate with a known excess of phthalic anhydride. The oil has a hydroxy group content of 5.16% by weight. Ex 7 - Ex 6 Open Ring ESO Acrylation With several changes, repeat Ex 2 to acylate Ex 6 Open Ring ESO. First, use 60 g (0.1819 hydroxy equivalent (OH)) of Ex 6 open ring instead of Ex 1 amide triol and 200 mL of toluene and reduce the amount of acryloyl chloride to 24.7 g (0.2183 mol). Also reduce the amount of N, N-diisopropyl ethylamine to 24.7 g (0.191 mol) but increase the addition time to 50 minutes while maintaining the ice bath at a temperature within a range of 6 ° C. at 9 ° C. Also, remove the ice bath after adding the second 50 mL aliquot of toluene and reduce the stirring time from 24 hours to 22 hours.

Recover the final product, a clear liquid, as in Ex 2. The liquid has a viscosity of 1.55 Pa. S (1550 cps); and FTIR analysis indicates that an acylate structure is present in the liquid. This Ex 7 produces an acylate-containing open ring ESO with an appropriately low operating viscosity of less than 4.0 Pa.s (4,000 cps). Trained technicians wish to minimize operating viscosity when possible, especially in paint applications.

Ex 8 - Preparation of UV-cured coatings using Ex 7 product

With a number of changes, repeat Ex 3. First use 18.38 g of Ex 7 product instead of Ex 2 product and increase the amount of IRGACURE ™ 500 to 0.50 g. Also, increase the amount of BYK ™ to three drops. The formulated coating solution has a viscosity of 1.525 Pa.s (1.525 cps).

Apply the coating solution formulated as in Ex 2, but use phosphate steel panels instead of aluminum panels, increase the irradiation temperature to 43 ° C (110 ° F) and decrease the cure rate to 2.54 m / s. Summarize the cured coating properties in Table 2 below.

Ex 9 Preparation of UV-cured coatings from a mixture of an epoxy acrylate and the product of Ex 7

Repeat Ex 4 with several changes. First, use 27.63 g of Ex 7 product instead of Ex 3 amide triacrylate and increase the amount of epoxy acrylate to 18.42 g. Also increase the amount of IRGACURE ™ 500 to 1.24 g, the amount of methyl diethylamine to 1.06 g, the amount of BYK ™ 307 to four drops and the amount of BYK ™ A-555 to six drops. In addition, apply the formulated coating solution as in Ex 8 instead of Ex 4 substrate and conditions. Summarize the coating properties in Table 2 below.

Ex Comp C

Repeat Ex Comp A, but change the amounts of epoxy diacrylate and acrylate each to 15.92 g, decrease the amount of IRGACURE ™ 500 to 0.86 g and methyl diethylamine to 0.73. Also, change the amounts of BKY ™ 307 and BKY ™ A-555 respectively to three drops and six drops. Diacrylate should be added to achieve a desirable operating viscosity less than or equal to 4.0 Pa.s (4,000 cps) when the epoxy acrylate has an undiluted viscosity (at 25 ° C) of 19 Pa.s (19,000 cps). In addition, apply and cure coatings as in Ex 8 rather than as Ex Comp A. Summarize the properties of cured coatings in Table 2 below. Report the impact resistance values determined in accordance with ASTM Method D 2 794 explained above in kilogram-meter (kg-m).

Table 2

<table> table see original document page 36 </column> </row> <table> The data in Table 2 shows that Ex 7 acylate-containing open-ring ESO provides improved impact resistance when used with a reactive diluent as in Ex 9 relative to a conventional acrylate diluent (tri (propylene glycol diacrylate) or TPGDA) as in Ex Comp C, even at higher viscosity. Although the ratio of reactive diluent to bisphenol A epoxy acrylate is about the same in both Ex 9 and Ex Comp C, the amount of reactive diluent (Ex 7) in Ex 9 is slightly higher relative to bisphenol A epoxy acrylate than in Ex Comp C for composition viscosity drop to 4.0 Pa.s (4,000 cps). An additional increase in the amount of Ex 7 reactive diluent relative to bisphenol A epoxy acrylate should lead to an additional decrease in composition viscosity. The data in Table 2 for Ex 8 also show that even without bisphenol A epoxy acrylate, an Ex 7 acylate-containing open-ring ESO-based cured coating provides impact resistance at least equal to that of a completely conventional coating. bisphenol A epoxy acrylate formulation as in Ex Comp C. The composition of Ex 8 may also be used when formulated in the absence of TPGDA or some other reactive diluent due to its low viscosity relative to that of bisphenol A epoxy acrylate.

Ex 10 - Preparation of a 12-hydroxymethyl stearate based amide triol

Weigh 200 g of 12-hydroxymethyl stearate (PARACIN ™ 1, CasChem from Rutherford Chemicals) and 276.0 g of diethanolamine in a 2000 mL three-neck round bottom flask equipped with heating mat, thermocouple, mechanical stirrer and a sprayer. Heat the flask and its contents to a setpoint temperature of 120 ° C. Maintain the contents of the flask at that temperature while mixing the contents and subjecting them to subsurface nitrogen purge for 30 minutes. Continue mixing but change subsurface purge to air purge and maintain these conditions overnight.

Allow the contents of the flask to cool to room temperature (nominally 25 ° C) and then add 1000 mL of chloroform to the flask to convert the contents to a chloroform solution. Wash the solution four times with 700 g of deionized water, then dry the solution with 75 g of magnesium sulfate (MgSO4). Isolate the product from solution via rotary evaporation as in Ex 1.0 product, a solid at room temperature weighs 216.7 g, equivalent to a yield of 88.6% of theory. Analysis of the product as in Ex 1 is consistent with an amide triol structure.

Ex 11 - Acrylation of Ex 10 amide triol Weigh 400 g of diethyl ether, 95.0 g of Ex 10 amide triol and 72.0 g of acryloyl chloride in a 2000 mL three-necked round bottom flask. It is immersed in an ice bath and equipped with an addition funnel, thermocouple, mechanical stirrer and a nitrogen air purge tube. Activate the mechanical stirrer to shake the contents of the balloon. Weigh 96.9 g of N, N-diisopropylethylamine into the addition funnel and feed it dropwise into the stirred contents over a 100 minute interval.

Remove the ice bath, add 250 g of diethyl ether to the flask to form a mixture and stir the mixture at room temperature overnight. Then add 150 µL of diethyl ether and 1000 mL deionized water to the flask and continue stirring for 60 minutes.

Transfer the contents of the flask to a separating funnel to phase separate into an aqueous layer and a liquid organic layer, then discard the aqueous layer. Wash the liquid organic layer twice with 170 g of a 5 wt.% Aqueous NaCl solution, twice with 170 g of a 5 wt.% Aqueous H2SO4 solution and finally twice with 170 g of a 5 wt. 5% by weight NaHCO3 before drying it with 25 g of MgSO4. Add 0.12 g of 4-methoxyphenol to the washed and dried organic liquid, then isolate a liquid product via rotary evaporation as in Ex 10. The liquid product weighs 97.8 g, representing a yield of 73.3% of theory, and has a viscosity of 0.25 Ps (250 cps). H NMR and FTIR analyzes of the product confirm the presence of an amide triacrylate structure. Ex 12 - Preparation of ricinolamide triol Repeat Ex 10 with several changes to prepare a ricinolamide triol. First, replace 200.1 g of castor oil with 12-hydroxymethyl stearate. Second, use 400 g of 5 wt% aqueous NaCl solution for each wash and decrease the amount of MgSO4 to 20 g. The recovered product weighs 195.5 g, representing a theoretical yield of 78.0%. 1H NMR and FTIR analyzes of the product are consistent with a tricinolamide triol structure.

Ex 13 - Acrylation of Ex 12 ricinolamide triol Repeat Ex 11 with changes. Start by weighing 200 g of diethyl ether, 47.5 g of Ex 12 product and 36.9 g of acryloyl chloride in a 1000 mL three-neck round bottom flask that is situated and equipped in the same manner as the 2000 flask. mL of Ex 11. Reduce the amount of N, N-diisopropyl ethylamine to 50.5 g and the amount of diethyl ether to 139 g.

Instead of the amounts of diethyl ether and deionized water and mixing time specified in Ex 11, add 96 g of diethyl ether and 500 g of a 3% by weight aqueous NaHCO3 solution and reduce the mixing time to 30 minutes.

After discarding the aqueous layer, change the product recovery procedure. Start by adding 210 g of diethyl ether to the organic layer to form a dilute organic layer, then wash the diluted organic layer three times with 150 g of a 5 wt% aqueous NaHCO3 solution before drying it with 10 g MgSO4. Remove half of the amount of 4-methoxyphenol added prior to product isolation by rotary evaporation. The product weighs 51.1 g, representing a theoretical 75.8% yield, and has a viscosity of 0.19 Pa.s (193 cps). 1H NMR and FTIR analyzes of the product are consistent with a ricinolamide acylate structure.

Ex 14 - Preparation of an amide triol from diethanolamine and 12-hydroxymethyl methyl stearate Preparing a product containing 12-hydroxymethyl methyl stearate by methyl oleate reducing hydroformylation using procedures outlined in US Patent No. 4,496,487, whose teachings here are incorporated to the fullest extent permitted by law. Subject that product to distillation to remove volatile components and produce a reagent with a 94% by weight 12-hydroxymethyl methyl stearate content based on the weight of the reagent.

Prepare an amide triol based on 12-hydroxymethyl methyl stearate by repeating Ex 10 with changes. Change the apparatus by replacing a condenser Dean-Stark siphon with a nitrogen air purge tube with the Ex 10 vaporizer. Weigh 400 g of reagent containing 94 wt% of 12-hydroxymethyl methyl stearate prepared above and 511, 7 g diethanolamine in the flask. Add a solution of 0.93 g of potassium hydroxide (KOH) in 10 mL of methanol (MeOH) before warming the contents of the flask to a setpoint temperature of 10 0C and maintain that temperature with stirring overnight. . Use a modified product recovery process over that of Ex 10. Start by replacing toluene with chloroform. Change the washing procedure by washing three times with 1600 g of a 2 wt% aqueous NaHCO3 solution and drying with 80 g instead of 75 g MgSO4. Recover the product via rotary evaporation under reduced pressure at a setpoint temperature of 600 ° C to produce a liquid weighing 450 g, representing a yield of 92.0% of theory. 1H NMR and FTIR analyzes of the product are consistent with an amide triol structure.

Ex 15 - Acrylation of Ex 14 amide triol Repeat Ex 11 with changes. Start by weighing 704 g of diethyl ether, 180.1 g of Ex 14 amide triol and 139.2 g of acryloyl chloride in the 2000 mL three-necked flask of Ex 11 apparatus. Increase the amount of Ν, Ν- diisopropyl ethylamine to 174 ° C, and add it as in Ex 11, but over a period of 220 minutes.

Remove the ice bath and stir the mixture at room temperature (nominally 25 ° C) overnight, but do not add any diethyl ether before stirring overnight. To stirring overnight, add 260 g of diethyl ether and 400 g of a 2% by weight aqueous NaCl solution to the contents of the flask. Modify the Ex 11 recovery procedure by saving both the aqueous layer and the organic layer after phase separation. Wash the organic layer four times with 400 g of a 5% by weight aqueous NaHCO3 solution and store the washed organic layer. With stirring, add 400 g of deionized water and 116 g of diethyl ether to the saved aqueous layer, then stop stirring and allow phase separation to occur in an aqueous layer and an ether layer in a separatory funnel. Wash the ether layer with 400 g of a 5 wt% aqueous NaHCO3 solution, allow the ether layer to stand overnight, then wash it three more times with 400 g of the aqueous NaHCO3 solution. Combine the washed ether layer with the saved washed organic layer and dry the combined layers with 30 g of MgSO4. Add 0.32 g of 4-methoxyphenol in the organic layer / dry ether combination and recover a liquid product via rotary evaporation as in Ex 11. The product has a viscosity of 0.25 Pa.s (250 cps) and per 1 H NMR and FTIR analyzes, it is consistent with an amide triacrylate structure.

Ex 16 - Preparation of an amide polyol from an open ring ESO

Repeat the Ex 10 process with changes to prepare an open ring ESO based amide polyol. Start by weighing 232.6 g of an open-ring epoxidized soybean oil prepared as in Ex 6 and 200.3 g of diethanolamine in the Ex 10 apparatus. Reduce the setpoint temperature to which the balloon and its contents are heated. at 100C.

After allowing the contents of the flask to cool to room temperature, add 600 mL toluene instead of 1000 mL chloroform to convert the contents to a toluene solution. Change the washing and drying procedure starting with two washes with 100 g of deionized water, continue with two washes with 1000 g of a 3 wt% aqueous NaCl solution before drying with 160 g of MgSO4. Isolate the product from the solvent (toluene) by rotary evaporation under reduced pressure at 60 ° C as in Ex 1. The isolated product weighs 209.7 g and, by 1H NMR and FTIR analysis, has a structure consistent with that of a polyol of amide. Ex 17 - Ex 16 Amide Polyol Acrylation Use Ex 13 apparatus and a modification of the procedure described herein to acylate Ex 16 Amide Polyol. Replace Ex 16 Amide Polyol with Ex 12 product and reduce amount of acryloyl chloride to 36.1 g. Reduce the amount of N, N-diisopropyl ethylamine to 47.9 g and feed it dropwise over a time period of 110 minutes.

After re-over the ice bath, add 150 g of diethyl ether with stirring and allow to stir continuously overnight at room temperature before adding another 150 g of diethyl ether along with 500 mL of deionized water while stirring for 45 minutes. minutes

After discarding the aqueous layer, use a modified procedure to recover the acylated amide polyol. First wash the organic layer twice with 110 g of a 5 wt% aqueous NaCl solution, then twice with 110 g of a 5 wt% aqueous sulfuric acid (H2SO4) solution and twice with a 5% by weight NaHCO3 before drying the organic layer with 15 g of MgSO4. Add 0.07 g of 4-methoxyphenol and isolate the product via rotary evaporation under reduced pressure and at room temperature to yield 46 g of product (69.8% theoretical yield). The product has a viscosity of 0.65 Pa.s (650 cps) and, by1 H NMR and FTIR analyzes, is consistent with an acylated amide polyol structure.

Ex 18 - Preparation of an acylate from a 12-hydroxymethyl methyl stearate-derived polyester In a 2 liter glass reactor vessel, charge 1050.3 g (3.15 moles) of soy monomer and 328.9 g ( 0.53 mol) of ethoxylated glycerine as initiator. Seal the container and degass it with a 2.67 kPa vacuum nitrogen gas spray while heating the contents of the container to a setpoint temperature of 50 ° C. Briefly stop the vacuum and add 0.78 g (565 ppm) of stannous octanoate to the container. Reset the 2.67 kPa vacuum, remove or disconnect nitrogen vaporization and heat the container and contents to a setpoint temperature of 195 ° C and keep the balloon and contents under such conditions for a period of 4 hours. , collect methanol byproduct (MeOH) in a dry ice trap. As an alternative, a vacuum, nitrogen spray or any combination of the two may also be used to effect MeOH removal. After the four hour period, release the vacuum and allow the reactor vessel and its contents to cool to room temperature overnight in nitrogen. Add 0.77 g (558 ppm container contents) of stannous octanoate and connect a nitrogen spray tube to the container. Heat the vessel and its contents to a setpoint temperature of 1950C with slow nitrogen spray for 4 hours to complete the reaction.

Using the same apparatus as Ex 17 and a modification of the Ex 17 process, synthesize a polyester acylate using the polyester prepared in the immediately preceding paragraph. Start the modified process by weighing 700 mL of toluene, 200 g of polyester (OH equivalent weight 398.6 (OH equivalent weight = 1701 divided by% hydroxy, with% hydroxy being determined via titration according to the method of ASTM Test D 4274)) and 54.5 g of acryloyl chloride in the container. Increase the amount of N, N-diisopropyl ethylamine to 68.1 g, but decrease the addition time to 100 minutes. Remove the ice bath as in Ex 17, but do not add any ingredients before stirring the mixture at room temperature overnight. Prior to separation, add 400 g of a 3% by weight aqueous NaCl solution to the container. After separation using the separation funnel, discard the aqueous layer as in Ex 17 and wash the organic layer (toluene) three times with 400 g of a 3 wt% aqueous NaHCO3 solution and once with 400 g of deionized water before drying the organic layer with 119.4 g of Na 2 SO 4. Add 0.29 g of 4-methoxyphenol to the washed and dried organic layer then isolate the toluene product by rotary evaporation as in Ex 17, but at a temperature of 40 ° C. The isolated product is a liquid weighing 188.8 g, representing a product yield of 83.1% of theory. The product has a viscosity of 0.55 Pa.s (550 cps) and has a structure consistent with a polyester acylate according to 1 H NMR and FTIR analyzes. a monoacylate from 12-hydroxymethyl methyl stearate Using the same apparatus as Ex 18 and a modification of Ex 18, prepare a mono-acylate from 12-hydroxymethyl methyl stearate. Start by weighing 700 mL of toluene, 200 g of 12-hydroxymethyl methyl stearate (prepared by methyl oleate reducing hydroformylation described above) and 66.1 g of acryloyl chloride in the container. Increase the amount of Ν, Ν-diisopropyl ethylamine to 82.8 g, but reduce the addition time dropwise via the addition funnel to 85 minutes.

Recover the product as in Ex 18, but increase the amount of Na 2 SO 4 to 127.6 g and decrease the amount of 4-methoxyphenol to 0.11 g. The recovered product weighs 231.5 g, representing a yield of 99.3% of theory, and has a viscosity of 0.012 Pa. S (12.5 cps). FTIR analysis of the product suggests a structure consistent with a monoacylate.

Example 20 - Preparation of a monoacylate from methyl 11-hydroxy undecanoate

Prepare a mono-acylate from methyl 11-hydroxy undecanoate using the same apparatus as Ex 19, but with several modifications of the Ex 19 procedure. Start the modified process by weighing 600 mL toluene, 200 g 11-hydroxy methyl undecanoate and 100.4 g of acryloyl chloride in the container. Increase the amount of α, β-diisopropyl ethylamine to 125.5 g and the addition time dropwise via the addition funnel to 140 minutes.

Recover the product as in Ex 19, but reduce the amount of Na 2 SO 4 to 103.3 g and increase the amount of 4-methoxyphenol to 0.12 g. Recover the product as in Ex 19. The resulting product weighs 244.5 g, representing a 99.0 percent yield of theory and has a viscosity of 0.01 Pa.s (10 cps). Add 0.12 g of 4-methoxyphenol to the toluene solution and isolate the product by rotary evaporation of the solvent under reduced pressure at 40 ° C. 244.5 g of product with a viscosity of 10 cps was recovered. FTIR analysis of the product suggests a structure consistent with a monoacylate.

The novel acylate materials of the present invention, especially those of Ex 11, 13, 15 and 17-20, have very low viscosities ranging from 0.01 Pa.s (10 cps) to 0.65 Pa.s (650 cps). ). Such low viscosities lead to improved processing in any of a variety of UV curable applications such as inks and coatings. These materials are believed to be hydrophobic, thereby making them water resistant and flexible with respect to commercially obtainable materials. As such, it is believed that these new acylate materials are suitable for use to enhance both processability and performance of existing oligomers such as bisphenol A epoxy acrylate. In addition, certain new acylate materials may effectively serve as a substitute for one or more more oligomers.

Similar results are expected with other acylate materials, particularly amide acylate materials, prepared in accordance with the teachings herein.

Claims (10)

Process for preparing a reactive unsaturated α, β acylate monomer composition comprising the following steps: (a) polymerizing at least one fatty acid or fatty acid ester, the fatty acid or fatty acid ester containing at least at least one reactive hydroxy moiety with a polyol initiator to form a hydroxy functional aliphatic polyester; (b) reacting the polyester of step (a) with an unsaturated acylating agent α, β to form a reactive α, β unsaturated acylate. Process according to Claim 1, characterized in that the polyol initiator is selected from glycerol, glycerol ethoxylate, poly (ethylene glycol) or poly (propylene glycol). Process according to either of Claims 1 and 2, characterized in that the fatty acid or fatty acid ester is partially hydroformylated prior to step (a), provided that such hydroformile partial hydroformylation is at least 80 per cent. unsaturation present in such fatty acid or fatty acid ester prior to partial hydroformylation. Process according to any one of claims 1 to 3, characterized in that the fatty acid is 12- (hydroxymethyl) stearic acid. Process according to any one of claims 1 to 3, characterized in that the fatty acid ester is methyl 12- (hydroxymethyl) stearate. Process according to any one of claims 1 to 5, characterized in that the unsaturated acylating agent α, β is at least one of ethyl acrylate, methyl methacrylate, or an acid halide selected from the group consisting of of acryloyl chloride or methacryloyl chloride. Reactive α, β unsaturated acylate, characterized in that it is prepared by the process as defined by any one of claims 1 to 6. UV curable composition, characterized in that it comprises reactive α, β unsaturated acylate as defined by claim 7. Coating composition, adhesive composition or UV curable ink, characterized in that it comprises the UV curable composition as defined by claim 8. Coating, adhesive composition or UV curable ink, characterized in that it is prepared from the corresponding composition as defined by claim 9.