MXPA00003169A - Process of preparing curable compositions and compositions therefrom - Google Patents

Abstract

The invention relates to a curable composition and a process of preparing the curable composition. The process comprises (a) forming an oligomer from oligomerization of a mixture of a monomer A having a functional group and a monomer B at a temperature in the range of from 150 DEG C to 650 DEG C, a pressure in the range of from 3 MPa to 35 MPa and the pressure is high enough to maintain the reaction mixture in a fluid state and a residence time in the range of from 0.1 second to 4 minutes;and (b) reacting a modifier having at least one reactive moiety with the oligomer through a reaction between the reactive moiety of the modifier and the functional group of the monomer A in the oligomer, and the modifier further comprises a curable group.

Description

PROCESS FOR PREPARING CURABLE COMPOSITIONS AND THE COMPOSITIONS SO PREPARED The present invention relates to a process for preparing curable compositions and compositions thus prepared. Oligomers, polymers with low degree of polymerization ("Dp"), of backbones containing acrylate or methacrylate units, are of commercial interest and have industrial uses in many different applications, such as adhesives, inks, coatings, films and others. A suitable low value of the Dp will supply a material with a sufficiently high molecular weight for reduced toxicity, and still sufficiently low for a low viscosity. However, the production of such oligomers has proved difficult and is often carried out by complicated and / or not very effective processes. It becomes even more difficult if an interlaxable or curable oligomer composition is desired for the applications. This is because the entanglement or healing property typically requires the presence of additional reactive groups suspended or pending in the oligomers. Such pending reactive groups may be, partially or substantially, removed or reacted and separated by unintended secondary reactions or premature entanglement reactions, during the oligomerization reaction. Several approaches have been tried and used to effect the production of such oligomers. For example, an approach uses chain transfer agents to control the Dp. As a result of the chain transfer chemistry involved, a chain transfer agent is incorporated into each skeleton structure of the oligomers. This makes the property of the oligomer much less uniform and more difficult to control. In addition, the most commonly used agents of chain transfer agents are mercaptans. Due to its odors and chemical properties. the use of such sulfur-based materials becomes increasingly socially difficult and environmentally less acceptable. Other common chain transfer agents, such as hypophosphites, bisulfites and alcohols, will also impart additional functionalities in the oligomers. Such additional functionalities may not be compatible with other ingredients in a product formulated or suitable for the intended applications. Removal of the additional functionality of the resulting oligomers can be difficult and / or expensive. Another approach requires the use of large amounts of initiators or catalysts. This approach adds the cost of the raw material to the production of oligomers. It can also result in unwanted degradations of the oligomer chain, branching and unintended or premature entanglement of the product before use. In addition, any residual catalyst or initiator in the product may have to be removed before the product can be used for many applications, to avoid compatibility or contamination problems. U.S. Patent No. 4,356,288 discloses the preparation of terminally unsaturated oligomers, with a Dp in the approximate range of 6 to 30, of esters of acrylic acid, by an anionic polymerization reaction, carried out in the presence of an catalytic amount of an alkoxide anion. Alkoxide anions are known to be sensitive to water. Therefore, the method is often adversely affected by the presence of moisture, which results in lesser performance and / or less uniformity of the oligomer product. Another US patent, No. 5,710,227, discloses a continuous high temperature polymerization process, for the preparation of terminally unsaturated oligomers, which are formed of acrylic acid and its salts, and acrylic acid and its salts with other unsaturated monomers ethylenically. High-temperature, continuous polymerization processes solve many of the problems associated with previously known methods, to prepare terminally unsaturated oligomers, formed from acrylic acid. However, the eta form of many of the acrylic acid products are solids at room temperature and, thus, require either heating and / or the addition of a solvent for the handling and use of the products. U.S. Patent No. 5,484,850 discloses copolymer compositions which are crosslinkable by a free radical method and have a molecular weight (Mn) of from 1500 to 6000 and a polydispersity of from 1 to. Copolymer A is composed of 50 to 85 mol% of a monomer (a) containing methacryloyl groups; from 15 to 50 mol% of another monomer (a2), capable of undergoing free radical polymerization; and from 5 to 50 mol% of the total amount of the monomers (al) and (a2), the monomers (a3) being functional groups selected from the group consisting of hydroxy, carboxamido, amino, carbonyl, isocyanate, carboxyl and epoxy, these functional groups are capable of undergoing a condensation or addition reaction. The polymerization is carried out at a temperature of 140 to 210 ° C and with an average residence time from 2 to 90 minutes. The copolymer A reacts with an olefinically unsaturated monomer B, which carries a functional group, which is complementary to the functional groups of the monomers (a3). The products are solid that tend to limit their employment and process options.

The present invention is directed to overcoming the problems associated with the previously disclosed methods for preparing oligomers, liquid oligomers, particularly curable or crosslinkable, by the provision of an oligomerization process that produces low Dp curable oligomers, in the range of 3 to 100. , without the need for excessive amounts of initiators. The curable oligomer products are in liquid form and may be terminally unsaturated. The crosslinkable or curable functionality is incorporated into the oligomer by a reaction after oligomerization - a post-oligomerization reaction - between the altered oligomer or oligomer with a modifier, which contains a crosslinkable / curable functional group. The present invention also provides curable oligomer compositions, prepared according to the disclosed process. Also, the invention provides curable oligomer compositions which are substantially free of metals, salts and / or surfactant contaminants. The product of the present invention is useful for a number of applications, such as films, markers, coatings, paints, adhesives, binders, inks and others. More specifically, the present invention relates to a process for preparing a curable composition, comprising forming an oligomer having a Dp in the range of 3 to 100, from the oligomerization of a mixture, which comprises a monomer A and a monomer B, under a first condition, in which monomer A has at least one functional group which either is generated after oligomerization or is present in monomer A prior to oligomerization and remains substantially unreacted during oligomerization; the oligomer has a first number of monomer units incorporated in its backbone; and wherein the first condition comprises a temperature in the range of 150 to 650 ° C and a pressure in the range of 3 to 35 MPa, which is sufficient to maintain the mixture in a fluid state, and a residence time to that temperature and - pressure in the range from 0.1 second to 4 minutes; and reacting a modifier having at least one reactive part, with the oligomer, through a reaction under a second condition between the reactive part of the modified and the functional group of monomer A incorporated in the oligomer, to produce the curable composition, where the modifier further comprises a curable group, selected from the group consisting of a carbon-to-carbon double bond, a heterocyclic oxygen-containing group, and mixtures thereof, and the curable group remains outstanding in the curable and crosslinkable composition, after the reaction .

The term "oligomer" used herein means a polymer composition which has a degree of polymerization (Dp) in the range of 3 to 100. Unless stated otherwise in the present application, the term " "polymerization" is used herein as a generic term and interchangeable with the term "oligomerization". An oligomer 'has a number of monomer units incorporated into the backbone. The degree of polymerization (Dp) is determined as an average number of the monomer unit. Depending on the oligomerization reaction mechanism, the actual number of carbon atoms in a particular oligomer backbone can be a number for or not, although the carbon-carbon double bonds in the monomers have two carbon atoms each. Since it is rare for all molecules of the oligomer to have the same total number of monomer units incorporated in the backbone, there is usually a distribution of several oligomers with lower Dp and / or. greater than the indicated and / or preferred range in the application. This type of distribution is also known to exist in almost all polymers and is commonly referred to as "polydispersity". a preferred Dp of this invention is in the range of 5 to 50. A more preferred Dp is in the range of 5 to 20. The present invention also relates to a curable composition., particularly by UV light, visible light electron beam methods, .prepared by a process comprising forming an oligomer with a Dp in the range of 3 to 100 from the oligomerization of a mixture, which comprises a monomer A and a monomer B, under a first condition, in which monomer A has at least one functional group which either is generated after oligomerization or is present in monomer A, prior to oligomerization and remains substantially unreacted during oligomerization; wherein monomer B is selected from the group consisting of ethylene, propylene, C4 to C10 α-olefins, butadiene, isoprene, styrene, substituted premiere, vinyl ester, vinyl ether, vinyl silane, vinyl halide, acid acrylic, methacrylic acid, crotonic acid, alkyl acrylate ester, alkyl methacrylate ester, alkyl crotonate ester, acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, and mixtures thereof; the oligomer has a first number of monomer units incorporated into its backbone; and wherein the first condition comprises a temperature in the range of 150 to 650 ° C and a pressure in the range of 3 to 35 MPa, which is sufficient to maintain the mixture in the fluid state, and a residence time at that temperature and pressure, in the range of 0.1 second to 4 minutes; and reacting a modifier having at least one reactive part with the oligomer through a reaction under a second condition between the reactive part of the modifier and the functional group of monomer A incorporated in the oligomer, to produce the curable composition, in which the modifier further comprises a curable group, selected from the group consisting of a carbon-carbon double bond, an oxygen-containing heterocyclic group, and mixtures thereof, and the curable group remains outstanding in the curable and crosslinkable composition, after the reaction. The word "slope" or "pendant" means a group, a functional group or a reactive part, which is not in the skeleton structure of an oligomer or polymer itself. A reaction of a pending group for the present invention will not cause any change in the structure of the skeleton itself. A pending group can be linked directly to a carbon atom in the skeleton structure of the oligomer. Examples of these pendant or pendant groups of the type which is directly attached include the group -OH or -OC (= 0) (CH3) (of the vinyl acetate monomer); and -COOH or -COO (R) (of acrylates or methacrylates). Or, there may be other intermediate chemical groups or parts between the functional group and the carbon atom in the skeletal structure, to serve as "linkers". An example of this type is the -OH group in the 2-hydroxyethyl methacrylates, when used as one of the monomers. There is a group -CH2CH2- between the group -OH and the group -C (= 0) -0-, of the structure of the skeleton. Other examples of linkers include - (-0-CH2CH2) n, where n is in the range of 1 to 10. Others will become apparent from the remainder of the description of the present invention. Pending groups for this invention are generally reactive, or they are suitable for attaching a crosslinkable or curable group to the oligomers, or they are sanitized for healing or entanglement. Healing and interlacing are used here interchangeably. For ease of understanding of the present invention, a general outline is summarized below. It is used only for purposes of illustration and is not intended to limit the scope of the invention, which is defined herein by the specification and the claims. It is also intended that some of the stages can be carried out simultaneously or sequentially. monomer A + monomer B? oligomer [? post-olgomerization generation of functional groups, optional]? reaction with a modifier to form a curable composition [- emulsion formation to obtain a curable formulation, optional]? healing or interlacing.

In the present invention, an oligomer is prepared by an oligomerization reaction of a mixture, the lime comprising a monomer A and a monomer B. The mixture may further comprise a solvent and other materials for a variety of purposes, such as catalysis or the reaction mediation. Monomer A and monomer B are preferably different, but they may be the same in certain specific cases, in which monomer A is produced by the transformation of monomer B incorporated in an oligomer, after the oligomerization reaction, as described below. in greater detail. Monomer A and monomer B can be pre-mixed, with or without a solvent, prior to oligomerization, or they can be introduced separately into a reaction zone at a predetermined rate or manner. The latter requires a mechanism to supply the appropriate mixture. This mechanism can be static, such as inputs, nozzles or specially designed moving parts, such as a mechanical agitator device. For the present invention, it is preferred to have the monomers and optionally a solvent, if present, pre-mixed prior to feeding to the reactor. For the present invention, monomer A must have, in addition to a polymerizable or oligomerizable, carbon-to-carbon double bond, a functional group which does not participate in, or remains pending or substantially unreacted during, the oligomerization reaction. Such a functional group may be present in monomer A itself, prior to oligomerization or may be generated after oligomerization from an "equivalent of monomer A". After the functional group is generated, the reaction between the modifier through its reactive part and the functional group of the oligomer can be carried out to form the curable composition. It is within the scope of the present invention to generate the functional group after oligomerization, from an "equivalent of monomer A", that is, after completion of the oligomerization or substantially complete. This requires the use of an "equivalent of monomer A" in the oligomerization reaction and at least one additional conversion reaction, to generate the desired functional group. It is also possible to have the additional conversion reaction and the oligomerization occurring almost simultaneously. An "equivalent of monomer A" is a compound that contains a carbon-to-carbon, monomeric, oligomerizable or polymerizable double carbon bond, which has another group that can be converted to produce the desired functional group, after completion of the oligomerization or polymerization or substantially complete during the oligomerization reaction. An "equivalent of monomer A" may be the same as the monomer B used in the oligomerization reaction. There are several reasons and benefits for using the "monomer A equivalent". For example, vinyl alcohol does not have a chemically stable monomeric form, which can be easily used in an oligomerization or polymerization reaction. Therefore, vinyl acetate is most frequently used as the "equivalent" of vinyl alcohol and the acetate group is converted by hydrolysis to generate the desired hydroxy (OH) group, upon completion of the oligomerization or polymerization reaction. If desired, the acetate group can also be converted to an acrylate or methacrylate group by means of a trans-esterification reaction or by hydrolysis followed by direct esterification. Another example of this type of generation follows the oligomerization of functional groups, particularly outstanding functional groups, where the "equivalent of monomer A" is the same as monomer B. For example, a homo-oligomer of methyl acrylate can be, partially or completely, hydrolyzed to form carboxylic acid groups, i.e., -COOMe groups. they are transformed into -COOH functional groups, by means of hydrolysis. Such functional groups can then be reacted with a modifier having a reactive part, such as glycidyl (meth) acrylate or the hydroxyalkyl ester of acrylic or methacrylic acid, to achieve the desired incorporation of curable carbon-to-carbon double bonds. Another example involves a co-oligomer prepared from different esters of ethylenically unsaturated acids. A typical co-oligomer can be obtained from methyl acrylate and n-butyl methacrylate. A hydrolysis reaction after oligomerization will also produce -COOH groups. An advantage of such generation after the oligomerization of functional groups is that the hydrolysis reaction can be controlled or adjusted to give the desired level or amount of functional groups in the oligomer products. Because different monomer units in the oligomer structure usually have different hydrolysis or transesterification regimes, this method provides another way to control the incorporation of the interlacing functionalities. Another type of generation, after oligomerization, of functional groups involves the hydrolysis of pending amide groups. Many compounds are suitable for their use as monomer A in the present invention. The selection depends primarily on the monomer B used and the reactive part in the selected modifier. Moriomer A must have at least one functional group that exists after or does not participate substantially in the oligomerization reaction.

General categories of such functional groups include the carbon-to-carbon double bond, halides, hydroxyalkyls, hydroxyaryl, carboxylic acids or esters, epoxides (or oxyranyls), oxetanyl, anhydrides, alkylsiloxy, alkoxysilyl and arylsiloxy. The anhydride-type groups may be in an incorporated form through the carbon-to-carbon double bond of the monomers, such as maleic anhydride, citraconic anhydride and itaconic anhydride. It will be understood that not all of the disclosed functional groups can be used for all different types of oligomerization reactions. It will also be understood that not all functional groups will react with the reactive portions of all modifiers. For the present invention, there must be a reasonable reaction rate between the functional group and the reactive part, under a second reaction condition, with or without a catalyst or reaction mediator. The chemical compatibility must also be satisfied. Specific limitations on functional groups and reactive parts are also revealed here. Examples of a monomer A suitable for the present invention include: acrylic acid, methacrylic acid, 1,3-butadiene, isoprene, 4-vinylcyclohexene, allyl alcohol, allyl esters such as allyl acetate, allyl propionate, allyl acrylate , allyl methacrylate, allyl crotonate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fluoride, vinyl acetate, vinyl benzoate, norbornadiene, substituted norbornadienes, 4-vinylcyclohexene oxide, glycidyl methacrylate, glycidyl acrylate, glycidyl crotonate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, methacrylate 4-hydroxybutyl, acrolein, methacrolein, maleic anhydride, itaconic anhydride, citraconic anhydride, vinyltrimethoxysilane, vinyltriethoxy-silane, vinyltrichlorosilane, allyltrichloride osilane, allyl-trimethoxysilane, allyltriethoxysilane, β-methacryloxypropyltrimethoxysilane, and mixtures thereof. Examples of an "equivalent of monomer A" include vinyl acetate, vinyl halide (such as vinyl chloride, vinyl bromide) , vinyl iodide, vinyl fluoride), vinylidene halide, allyl acetate, allyl propionate, methacrylonitrile, acrylonitrile, C 1 -C 4 alkyl acrylate esters, CLC alkyl methacrylate esters, alkyl crotonate esters C1-C20, N-substituted acrylamide and acrylamides, such as N-methylacrylamide, methacrylamide and N-substituted methacrylamides, such as N, N-dimethylmethacrylamide, and mixtures thereof. The corresponding functional groups generated are of the -OH type (vinyl acetate and allyl acetate) and -COOH (others), respectively. Depending on the desired products, certain monomers A, such as maleic anhydride, itaconic anhydride and citraconic anhydride may also serve as an "equivalent of monomer A" to produce functional groups of the dicarboxylic acid. Monomer B is typically an ethylenically unsaturated monomer and its derivatives, such as olefins, styrenes, unsaturated carboxylic acids, esters and amides, vinyl esters, vinyl ethers, vinyl silanes and mixtures thereof. A preferred monomer B comprises α, β-ethylenically unsaturated carboxylic acids and their linear or branched alcohol esters, containing from 1 to 20 carbon atoms. Specific examples of monomer B include, but are not necessarily limited to, ethylene, propylene, α-olefins C4-C10, 1, 3 -butadiene, isoprene, styrene, substituted premieres, such as p-methylstyrene, vinyl acetate, vinyl benzoate, vinyl chloride, vinyl bromide, allyl acetate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl crotonate, ethyl acrylate, ethyl methacrylate, ethyl crotonate, n-propyl acrylate, n-propyl methacrylate, n-propyl crotonate, propyl acrylate, i-propyl methacrylate, i-propyl crotonate, n-butyl acrylate, n-butyl methacrylate, crotonate n-butyl, sec-butyl acrylate, sec-butyl methacrylate, sec-butyl crotonate, ethyl 4,4,4-trifluorocrotonate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl crotonate, acrylic acid, methacrylic acid, crotonic acid, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, ethyl vinyl ether, n-propyl vinyl ether , n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl vinyl ether, 2-chloroethyl vinyl ether, 2-aminoisobutyl vinyl ether, vinyltrimethylsilane and mixtures thereof. When the desired functional groups are already present in monomer A and remain substantially unreacted or pending during and after the oligomerization, the molar ratio of monomer A to monomer B, incorporated in the backbone of the oligomer produced, is in the range of 1. : 40 to 40: 1, preferably in the range of 1:20 to 20: 1, more preferably in the range of 1: 5 to 5: 1. When the functional groups are generated after the oligomerization from the "equivalent of monomer A", incorporated in the oligomers, the ratio of the number of functional groups generated to the number of total monomer units in the oligomer backbone is in the range of 1. : 100 up to 1: 1. It is also within the scope of the present invention, is the "equivalent of monomer A" can be converted into more than one functional group, ie the number z of groups, if a monomer has a maleic anhydride group which can be converted in two carboxylic functional groups per monomer unit. The ratio can exceed 1: 1 to 1.5: 1 or to a maximum of 2: 1. The oligomerization reaction is carried out under a first condition, which comprises a temperature of at least 150 ° C, generally in the range of 150 to 650 ° C, preferably in the range of 200 to 500 ° C, more preferably 275 at 450 ° C, and a pressure in the range of 3 to 35 MPa, preferably in the range of 20 to 30 MPa. A preferred combination of temperatures and pressures is in the ranges of 150 to 400 ° C and pressures of 16 to 32 MPa, respectively A more preferred combination of temperatures and pressures is in the ranges of 180 to 350 ° C and 20 to 27 MPa, respectively At a given temperature, it is more preferred to use a sufficiently high pressure to maintain the reaction mixture at the reaction temperature, with or without a solvent, in a fluid state, typically a liquid state or a fluid state Supercritical When a completely fluid, or liquid or supercritical state is preferred, it is within the scope of the present invention that a substantially fluid state can be used.Compounds such as water, C02 or ethylene can be maintained as a supercritical fluid. residence time is generally in the range of 0.01 second to 20 minutes, preferably in the range of 0.1 second to 4 minutes, more preferably in the int eve of 0.5 second to 2 minutes, and especially preferred, in the range of 1 second to 1 minute. The "residence time" is defined herein as the time when the mixture comprising the monomers is spent under the first oligomerization condition. A solvent or mixture of solvents is not required, but can optionally be used as a means for the oligomerization reaction. They are referred to here, collectively and interchangeably, as the "solvent", "solvents" or "solvent mixture". A solvent selected for a particular oligomerization reaction should not interfere with the desired oligomerization reaction not substantially reacting with the functional group present or on either of the monomers or on the oligomer product. It is preferred that the solvent can be easily separated or removed from the reaction products by such methods as distillation, phase separation, or evaporation. If a catalyst, mediator or initiator is used, it is preferred to have a solvent in which the catalyst or initiator is soluble in a used amount.

A mediator is a compound which, while or is capable of catalyzing the reaction, can nevertheless influence the reaction in some desired way. Examples of a solvent suitable for use in an oligomerization reaction include, but are not necessarily limited to, ethylene, pentane, hexane, heptane, octane, benzene, toluene, xylene (s), carbon dioxide, water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexyl formate, ethyl acetate and mixtures thereof. Examples of initiators, if present, include hydrogen peroxide, alkylhydroperoxide, such as t-butyl hydroperoxide and t-amyl hydroperoxide, alkyl peroxides, such as di-t-butyl peroxide, peracids, peresters, percarbonates, persulphates, ketone peroxides such as methyl ethyl ketone peroxide, oxygen, azo initiators and mixtures thereof. In cases where the functional groups are generated by at least one reaction after the oligomerization, such a post-oligomerization reaction is carried out under a condition of generation of functional group, which is known to those skilled in the art. Such post-oligomerization reactions include, but are not necessarily limited to, the hydrolysis, esterification, transesterification and ring opening reaction of the epoxide. The reaction can be carried out in a solvent and / or in the presence of a catalyst. For example, in a hydrolysis, esterification or transesterification reaction, an acid catalyst or a basic catalyst is typically used. The reaction between the functional group of the oligomer and the reactive part of a modifier is carried out under a second condition, which depends on the functional group, the reactive part, the solvent (if present) and other physical and chemical properties of the oligomer and the modifier. The second condition comprises a temperature in the range of 0 to 450 ° C and a residence time in the range of 0.1 second to 120 hours. The pressure is generally not a critical parameter, unless the modifier has a relatively high vapor pressure at the reaction temperature. Therefore, a wide range of pressures can be used. Room temperature is more convenient for many of these reactions. If necessary, a pressure in the range of 1 kPa (around 0.01 bar) up to 35 MPa (350 bar) can be used. To the extent that such reaction conditions are disclosed in U.S. Patent Nos. 4,059,616, 4,133,793 and 4,208,313, they are incorporated herein by reference. This reaction between a functional group and a reactive part can be carried out conveniently in the air, if there are no substantial secondary reactions, or production of by-products. Sometimes, oxygen air needs to be present in order to allow certain inhibitors, such as hydroquinone, to be used effectively. Optionally, a different non-reactive atmosphere can be used, particularly if the air could interfere with the reaction and / or cause any of the components to decompose or deteriorate. Examples of gases for supplying such a non-reactive atmosphere include, but are not necessarily limited to, nitrogen, argon, helium, or mixtures thereof. Gases, such as carbon dioxide, can also be used alone or in conjunction with the non-reactive atmosphere described above, if such gases do not interfere with the reaction and / or cause any of the components to decompose or deteriorate. Unlike the products of the prior art, the oligomers prepared according to the process of the present invention are, in general, terminally introduced. If desired, the installed terminals can be subjected to further reactions, such as hydrogenation, epoxidation or a number of other addition reactions known in the art. A suitable modifier for the present invention depends on the nature of the functional group. They are described below in more detail. In general, the modifier must have at least one reactive part, which will react with the functional group. Another requirement of a suitable modifier is that it must have an interlacing group selected from the group consisting of the carbon-carbon double bond (C = C), a heterocyclic group containing oxygen, and mixtures thereof, in which the crosslinkable group remains pending or substantially unreacted after the reaction between the modifier and the oligomer, through the reactive part and the functional group, respectively. Examples of a reactive portion in a suitable modifier include, but are not necessarily limited to, the C-OH (hydroxyalkyl group), -C (= 0) OH, -C (= 0) OR, -C (= 0) X, heterocyclic group containing oxygen and its mixtures. R is selected from the group C1 to C15 alkyl or an aryl group. Examples include, but are not necessarily limited to: 2-ethylhexyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, phenyl, and mixtures thereof. X is selected from the group consisting of chloride, bromide and iodide. Examples of a heterocyclic oxygen-containing group include the oxiranyl, oxetanyl and 1,3-dioxolanyl groups, of the following formulas: where R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from the group consisting of H and C to C8 alkyl groups, H is preferred for all "T" groups. It is also preferred to have two of the R1, R2 and R4 as H and the other as CH3. Examples of modifiers include, but are not necessarily limited to, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate. , 4-hydroxybutyl methacrylate, cinnamic acid, methyl cinnamic acid, acrylic acid, methacrylic acid, crotonic acid, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methyl crotonate, ethyl acrylate, ethyl methacrylate, ethyl crotonate, n-propyl acrylate, n-propyl methacrylate, n-propyl crotonate, n-butyl acrylate, n-butyl methacrylate, n-butyl crotonate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, crotonate 2-ethylhexyl, acryloyl chloride, methacryloyl chloride, crotonyl chloride and mixtures thereof, with the proviso that the respective modifiers are chemically compatible with each other in the mixtures. The following reactions between the oligomer and the modifier are within the scope of the present invention, when functional groups are present in monomer A, prior to oligomerization, or they are generated after oligomerization of any of the "monomer A" equivalent. "or the monomer B units, incorporated in the skeleton structure of the oligomer.

I. When the functional group is composed of hydroxy (-OH) groups, the reactive parts of the modifier are selected from the group consisting of ethylenically unsaturated carboxylic acids, esters of these ethylenically unsaturated carboxylic acids, acid halide derivatives of ethylenically unsaturated carboxylic acids , and its mixtures. Examples of monomer A in this group include, but are not necessarily limited to allyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl crotonate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, crotonate 3-hydroxypropyl, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl crotonate, and mixtures thereof. Examples of monomer A equivalents include allyl acetate, allyl propionate and vinyl acetate. Examples of a modifier include, but are not necessarily limited to, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid, methyl cinnamic acid, 2-ethylhexyl acrylate, methacrylate 2 -ethylhexyl, methyl crotonate, ethyl acrylate, ethyl methacrylate, ethyl crotonate, n-propyl acrylate, n-propyl methacrylate, n-propyl crotonate, i-propyl acrylate, i-propyl methacrylate, crotonate of i-propyl, n-butyl acrylate, n-butyl methacrylate, n-butyl crotonate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl crotonate, and mixtures thereof, acryloyl chloride, chloride of methacryloyl, crotonyl chloride, methacrylic anhydride, and mixtures thereof.

II. When the functional group is selected from the group consisting of epoxides (oxiranyl) and carbon-carbon double bonds, and the modifiers consist essentially of a compound, selected from an ethylenically unsaturated carboxylic acid or mixtures thereof, and an ethylenically unsaturated alcohol or its mixtures Examples of a monomer A in this group are 1,3-butadiene, 1,2-epoxide, glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, l-vinyl-4-cyclohexene epoxide, 1,3-butadiene, isoprene, l-vinyl-4-cyclohexene, norbutadiene, and mixtures thereof. Examples of a modifier include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid, methyl cinnamic acid, and mixtures thereof. Other suitable modifiers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl crotonate, 3-hydroxpropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl crotonate, 4-hydroxybutyl acrylate, 4-hydroxyethyl methacrylate. -hydroxybutyl, 4-hydroxybutyl crotonate and their mixtures. 2-ethylhexylolacrylamide can also be used as a modifier.

III. When the functional group is selected from the group consisting of the anhydride, alkoxysilyl, and mixtures thereof, the modifier is selected from the group consisting of hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, and mixtures thereof. Examples of monomer A in this group include, but are not necessarily limited to, maleic anhydride, itaconic anhydride, citraconic anhydride, α-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, allyltriethoxysilane, allyltrichlorosilane, vinyl crotonate, and mixtures thereof. Examples of modifiers include, but are not necessarily limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl crotonate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl crotonate, acrylate. of 4-hydroxybutyl, 4-hydroxybutyl methacrylate, 4-hydroxybutyl crotonate, and mixtures thereof.

IV. When the functional group is selected from the group consisting of hydroxyl (COH), carboxyl (COOH), amino (NH2) and substituted amino (NHR or NR'R "), the reactive part of a modifier consists essentially of an oxiranyl group. Examples of a preferred monomer A are selected from the group consisting of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, and mixtures thereof Examples of a modifier include glycidyl acrylate, glycidyl methacrylate, and glycidyl crotonate.

V. When the functional group is selected from the group consisting of an anhydride group, the reactive part of a suitable modifier can be an oxiranyl group. Examples of a monomer A include maleic anhydride, citraconic anhydride, itaconic anhydride, and mixtures thereof. Examples of a suitable modifier include glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, and mixtures thereof.

VI, When the functional group is selected from the group consisting of an aldehyde or ketone group, the reactive part in a suitable modifier is preferred to contain a hydroxyalkyl group. Examples of monomer A include acrolein, methacrolein, methyl vinyl ketone, and mixtures thereof. Examples of a suitable modifier include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl crotonate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl crotonate, 4-hydroxybutyl acrylate, methacrylate. of 4-hydroxybutyl, 4-hydroxybutyl crotonate, and mixtures thereof.

VII. When the functional group is a vinyl group, as part of an ether, no reaction with a reactive part is necessary when the curing method is selected from electromagnetic radiation. Examples of monomer A include, but are not necessarily limited to, vinyl acrylate, vinyl methacrylate, vinyl crotonate, and mixtures thereof. Examples of monomer B include, but are not necessarily limited to, ethylene, propylene, C4 to C10 olefins, butadiene, isoprene, styrene, substituted styrene, such as p-methylstyrene, vinyl ester, vinyl ether, silane vinyl, such as vinyltrimethylsilane, vinyl halide, acrylic acid, methacrylic acid, crotonic acid, alkyl acrylate or methacrylate, or crotonate ester, such as 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, ethylhexyl, ethyl acrylate, ethyl methacrylate, ethyl crotonate, n-propyl acrylate, n-propyl methacrylate, n-propyl crotonate, n-butyl acrylate, n-butyl methacrylate, n-butyl crotonate, and mixtures thereof, acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, and mixtures thereof.

VIII. When monomer A is selected from vinyl chloride, vinyl bromide, vinyl acetate, vinyl benzoate, vinylidene halide (such as chloride or fluoride) and mixtures thereof, the modifier comprises a metal salt of an unsaturated acid or a mixture of such salts. Examples of such unsaturated acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid, methyl cinnamic acid and mixtures thereof, the metal (ion) is selected from the group consisting of metals selected from Groups IA (Li, Na, K, Rb, C), IIA (Be, Mg, Ca, Sr, Ba), IIIA (Al, Ga, In, Tl) and mixtures of the Periodic Table (see the internal front cover of CRC Handbook of Chemistry and Physics, 76 to Ed. 1995-1996, DR Lide, Editor in Chief CRC Press, Inc. 1995). Examples of such salts include, but are not necessarily limited to, potassium acrylate, potassium methacrylate, potassium crotonate, sodium acrylate, sodium methacrylate, sodium crotonate, potassium acrylate, potassium methacrylate, potassium crotonate, acrylate. rubidium, rubidium methacrylate, rubidium crotonate, cesium acrylate, cesium methacrylate, cesium crotonate, magnesium acrylate, magnesium methacrylate, magnesium crotonate, aluminum acrylate, aluminum methacrylate, aluminum crotonate, and mixtures thereof . It is preferred to use phase transfer catalysts (PTC) in this case, to achieve reasonable reaction regimes. PTC can be obtained by choosing the appropriate phase transfer catalysts. Depending on the catalyst selected, the amount of the phase transfer catalyst used is, based on the total moles of the modifier present, in the range of 0 to 50 mol%, preferably in the range of 0.001 to 25 mol%, more preferably in the interval from 0.01 to 20 mole%. Typical phase transfer catalysts include, but are not limited to, the ammonium, phosphonium, arsonium, antimony, bismutonium and tertiary sulfonium salts, crown esters. For the salts, examples of suitable counter ions include, but are not necessarily limited to, the hydroxide, halide, sulfate, bisulfate, phosphate, nitrate, and mixtures thereof. Examples of such catalysts include tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium bisulfate, tetra-n-butylammonium hydroxide, tetraethylammonium bromide, tetramethylammonium bromide, tetrachloromethyl bromide, n-propylammonium, monomethyltrioctylammonium chloride [Aliquat 336], benzyltriethylammonium bromide, hexyltriethylammonium bromide, octyl triethylammonium bromide, cetyl trimethylammonium bromide, tricaprylmethylammonium bromide, phenyltrimethylammonium bromide, bromide tetraphenylphosphonium, triphenylmethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylarsonium bromide, pyridyl-butyl bromide, cetylpyridinium bromide, dicyclohexane-18-crown-5-ether; 18corona-5 and its mixtures. A reference in the area is Phasae Transfer Catalysis: Fundamentalis, Aplications, and Industrial Perspecti is, for C. Stark, C. Liotta and M. Halpern, Chapman & Hall, New York (1994). "Aliquat" is a registered trademark of General Mili, Inc.

IX. When the functional group in monomer A is an epoxide (oxiranyl) group, examples of a monomer A include glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, monoglycidyl maleate, monoglycidyl fumarate, and mixtures thereof. Examples of monomer B include, but are not necessarily limited to, ethylene, butadiene, isoprene, styrene, p-methylenetene, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl crotonate, ethyl acrylate, methacrylate ethyl, ethyl crotonate, n-propyl acrylate, n-propyl methacrylate, n-propyl crotonate, n-butyl acrylate, n-butyl methacrylate, n-butyl crotonate, 2-ethylhexyl acrylate, methacrylate 2-ethylhexyl, 2-ethylhexyl crotonate, a vinyl ester, such as vinyl acetate, a vinyl ether, such as vinyl ethyl ether, vinyl n-propyl ether, vinyl n-butyl ether, vinyl silane, such as vinyltrimethyl silane, and mixtures thereof. The curing method is selected from the group consisting of acid curing, base curing, acid generation by electromagnetic irradiation, selected from the group consisting of ultraviolet, visible light and X-ray irradiation, gamma irradiation (?) and combinations thereof, to produce a cured product of the radiation curable composition.

Preferred oligomer compositions (monomer A and monomer B) and corresponding modifiers include, but are not necessarily limited to, those listed in the following Table 1: Table 1 the monomer equivalents are in parentheses; AA. acrylic acid, GA: glycidyl acrylate; GMA: glycidyl methacrylate; BD: butadiene; IP: isoprene; MAA: methacrylic acid; HBA; 4-hydroxybutyl acrylate; HEA: 2-hydroxyethyl acrylate; MMA: methyl methacrylate; MA methyl acrylate; VOH: vinyl alcohol; VaC: vinyl acetate; VTMO: vinyltrimethoxysilane; MAN: maleic anhydride. b. n-butyl acrylate; BVE: n-butyl. vinyl ether; MMA: methyl methacrylate c.) Acrylic acid; GA: glycidyl acrylate; GMA: glycidyl methacrylate; HEA: 2-hydroxyethyl acrylate; AOPA: acrylpropionic acid; ICEMA: isocyanatoethyl methacrylate. d. after the acetate group was hydroxylized.

It is also within the scope of the present invention that the oligomers, after reaction with the modifier, can be dispersed or emulsified in a solvent consisting essentially of water, to form a formulation containing water, which can be used and cured, with the proviso that there is a reasonable chemical and physical stability of the composition of such a formulation that carries water. It is generally required to have a surfactant in the formulation. Many surfactants known to those skilled in the art can be used, including, but not limited to, the anionic, cationic, amphoteric and nonionic surfactants. Some specific examples include Triton X-100 and Triton X-200"Triton" is a registered trademark owned by Union Carbide Chemicals & Plastics Technology Corporation.) The terms "curable" and "crosslinkable" are used interchangeably herein, to mean that a sloping double bond or an oxygen-containing heterocyclic group may also be reacted / entangled under a set of suitable conditions and in the presence of a parameter selected from the group consisting of a catalyst, an energy source, a free radical source, an acid, a base or combinations thereof. The curable compositions can be cured (entangled) by a method number. Examples of such methods include, but are not necessarily limited to, electromagnetic irradiation, such as UV (UV) irradiation, visible light irradiation (VIS), irradiation? and X-ray irradiation (X-rays), irradiation of electron beams (E-beams), chemical or thermal generation of free radials, electrochemical generation of free radicals, photochemical generation of free radicals and their combinations. For irradiations of E and / or electromagnetic beams, such as UV / VIS irradiation, as curative methods, the curable composition may further comprise one or more photoinitiators such as one or more additives, which function as free radical initiators, cationic initiators. or anionic initiators. A general reference for photo-generations of free radical and photoinitiators can be found in Chapter 5 of Photogeneration Of Reactive Species For UV Curing "by C.

Roffey, John Wilety & Sons, New York, NY (1997). In the extent that the reference discloses several suitable photoinitiators and / or photo-generators of free radical, it is incorporated herein by reference. Acids or electromagnetic irradiation, (such as UV and / or VIS irradiation) to generate acids or bases, can be used for the curing of a composition having oxygen-containing heterocyclic groups, such as oxirane, oxetanyl or 1, 3-dioxolanil, E-beams, UV and / or VIS irradiations are three of the preferred healing methods. The curable compositions, particularly may further comprise one or more diluent monomers as other additives, with or without one or more photoinitiators. Such diluent monomers may or may not be the same as one or more of the monomers that have already been incorporated into the backbone of the oligomers. Many monomers or their mixtures, used to form the oligomers, can serve in the function as "diluent monomers". The diluent monomer can be used to reduce the viscosity, - providing solvency, and / or providing desired properties in addition to the final cured product, particularly to produce a product cured by electromagnetic irradiation. A general reference of such diluent monomers, sometimes referred to as reactive monomers in the curing composition, can be found in Chapter 6 of Photogeneration Of Reactive Species For UV Curing, by C.

Roffey, John ilety & Sons, New York, NY (1997). Table 2 provides a simplified general guidance line for selecting the various components: Table 2 to . ) Oligomers are required for all methods b. ) See text for the definition of "monomers" (diluent monomers) Generally, a UV source has a wavelength in the range of 180 to 400 nm. A visible light source (VIS) has a wavelength in the range of 400 to 700 nm. Information regarding EB can be found in Radiation Curxng In Polymer Science and Technology-Volume, Ed.- J. P. Fouasser and J. F. Rabek, Elsevier Applied Science, New York, 1993. Information regarding photoacids can be found in Radiation Curing In Polymer Science and Technology - Volume II, Ed. J.P. Fouassier and J. F. Rabek, Elsevier Applied Science, New York, 1993 and in Prog. Polym Sci., Vol. 21, pages 1-45, nineteen ninety six. For all reactions involved in the process discussed herein, it will be understood that they may be carried out individually in a continuous mode, a semi-continuous mode, an intermittent mode, a continuously stirred tank reactor, or a combination thereof. The various stages of the process can be carried out in the same or in different reactors. It is preferred to carry out the oligomerization reaction in a continuous mode. The geometry of the reactor and / or the residence time can be adjusted to provide flow rates to control product performance, product composition and / or product properties. Such information is available in many references. One such reference is U.S. Patent No. 5,710,227 (supra). Alternatively, some of the reactions may be carried out simultaneously in a continuous mode, a semicontinuous mode, an intermittent mode, a continuously stirred tank reactor mode, or a combination thereof. While it is generally preferred to recover the product of each individual reaction of the above process, to conduct the next reaction, the present invention will also work with minimal or no recovery or without purification. For example, it is not required to recover / separate the oligomers prior to the reaction with a modifier to produce curable compositions or carry out the post-oligomerization generation of the functional groups. In the case where the charges of the monomers and the modifier are at the same time, there is no need for any intermediate purification or separation. Typical methods of recovery or purification include, but are not necessarily limited to, distillation, extraction, filtration, centrifugation, sedimentation, solvent removal, removal of residual monomers, removal of residual modifier, catalyst removal and combinations thereof. The present invention also relates to a curable composition, prepared in accordance with the disclosed process. In particular, the curable composition comprises an oligomer having a degree of polymerization (Dp) of from 3 to 100, which has reacted with a modifier after forming the oligomer, in which this oligomer was prepared from a monomer A and a monomer B The composition may further comprise a free monomer, selected from any of the monomers disclosed herein. This free monomer may or may not be the same as any of monomer A or monomer B in the oligomer. Preferably, the curable composition consists essentially of (a) an oligomer with a Dp in the range of 3 to 100, which has reacted with a modifier, after forming the oligomer, where this oligomer is prepared from a monomer A and a monomer B , (b) a free monomer, selected from any of the monomers disclosed herein, (c) an initiator. The free monomer may or may not be the same as either monomer A or monomer B in the oligomer. The following examples are intended to illustrate the invention only. They should not be construed as limiting the scope or spirit of the present invention, which is defined only by "the claims and the specification disclosed herein." Example I - Oligomerization An oligomer of the present invention can be prepared according to the following procedure: A 3.3 meter long section of stainless steel pipe. , which has an internal diameter of 1.6 mm and a wall thickness of 1.27 mm, was connected at one end to a high-pressure pump (Hewlett Packard, Model HP 1050 TI) and at the other end a retro- Pressure Between the two ends, the pipe section was wound around a metal mandrel in the configuration of a torus The mandrel was placed on top of a primary coil of a transformer, so that the pipe coils and the mandrel would function as Transformer secondary coils The coils of the pipeline were also equipped with one end of a temperature probe The other end of the temperature probe was connected to a device olador of the temperature. This temperature controller device regulated the current supplied to the primary coil of the transformer, which had the effect of regulating the heat of the inductance imparted to the rolled steel pipe. A mixture of a monomer A and a monomer B (a few specific examples are shown below in Table 3) was used in the synthesis reaction of the oligomer. The mixture may further comprise an initiator and optionally a solvent. Nitrogen was bubbled through the mixture while stirring. If a solvent is not used, the initiator and the monomers are fed separately into the reactor. In a typical experiment, a suitable solvent was pumped in and through the pipeline by a high pressure pump at a previously set rate, in the approximate range of 0.05 to 10 milliliters per minute (ml / min). The pressure was maintained at a level of 20 MPa (200 bar) up to 35 MPa (350 bar). Electric current was supplied to the primary coil of the transformer to increase the temperature inside the pipe to a desired oligomerization temperature. The stream was then adjusted to maintain that temperature during the oligomerization reaction. After about 15 minutes, the solvents were pumped through the pipe and replaced by the reaction mixture, which was pumped continuously through the pipe at the same previously established regime, while maintaining the desired temperature and pressure. After a period of time for the solvent to be completely replaced from within the pipe, the effluent from the back-pressure control device was collected as the product. After supplying the mixture, or the individual monomers, they were exhausted, a solvent was pumped through the pipe, at the same current rate, temperature, and pressure. Any solvent and / or residual monomer was removed from the product in a rotary evaporator. The products in Table 3 were analyzed by various analytical methods - molecular weights by gel permeation chromatography (GPC); : structure and comonomer ratio by proton and carbon NMR spectroscopies; and terminal groups by the NMR spectrum or matrix-assisted laser desorption mass spectroscopy (MALDI-MS) Table 3 # The polymerization degrees (Dp) were: A, 8.2, B, 8.6, C, 8.5, D, 7.9, E, 8.5 * Average number of monomer units per oligomer. HBA: 4-hydroxybutyl acrylate; HEA hydroxyethyl acrylate; GA: glycidyl acrylate; GMA glycidyl methacrylate; BA: n-butyl acrylate Example II - Reaction of a Modifier with an Oligomer The equipment used was a 250 ml three-necked round bottom flask equipped with a reflux condenser, an overhead stirrer, a gas inlet tube and a thermal stopper. . The flask was charged with: (a) 137.06 grams of an oligomer having a composition of 38:62 (mole%) of GMA (glycidyl methacrylate, monomer A) to EA (ethyl acrylate, monomer B), a Dp of 6.5 and 23,000 ppm residual GMA, (b) 40.0 grams of acrylic acid, (c) 0.2 gram Cordova Accelerator AMC-2 (2-ethylhexanoate chromium), and (d) 0.26 grams of a 10% solution (weight ) of Actrene [registered trademark of Exxon Corporation] in propylene glycol-methyl-ethyl-ether. The mixture in the flask was stirred and heated under dry nitrogen at 90 ° C for 6 hours. No GMA residue was detected after this period. The reflux condenser was then replaced with a distillation head and any unreacted AA was removed by distillation under reduced pressure, with a hose vacuum. Other examples where the modifier was acrylic acid (AA) were: Table 4 * Average number of monomer units per oligomer. HBA, 4-hydroxybutyl acrylate; HEA, hydroxyethyl acrylate; GA, glycidyl acrylate, GMA, glycidyl methacrylate; BA-n-butyl acrylate # Dp: A2, 8.2; B, 8.6; C2, 8.5; D2, 7.9 Example III - Reaction of a Modifier with an Oligomer The equipment used is a 100 ml three-necked round bottom flask equipped with a reflux condenser, a magnetic stir bar, an air inlet tube and a thermal. The flask was charged with 41.1 grams of an oligomer having a composition of 20:80 (mole%) of AA (acrylic acid, monomer A), to BA (n-butyl acrylate, monomer B) and an Mn of 1204. With stirring, the flask and the oligomer were heated to about 100 ° C under an echo air purge for a period of 15 minutes. The mixture was cooled to room temperature for 30 minutes under a dry air purge, followed by the addition of 16.31 grams of GMA, 20 grams of ethyl acetate and 0.06 gram of Cordova Accelerator AMC-2 (chromium 2-ethylhexanoate) . While stirring under a dry air purge, the mixture was heated at about 85 ° C for five hours. Then it was cooled to room temperature. The residual GMA was found to be 2300 ppm.

A 0.25 g portion of the 2- (ethylamino) ethanol was added to the flask and the mixture was heated at 65 ° C for 20 minutes, cooled to room temperature and allowed to stand for 4 days. The residual GMA was found to be 150 ppm. To this were added 20.0 grams of acetic acid and 10.0 grams of ethyl acetate. The mixture was heated at 80 ° C for 8 hours. No residual GMA was detected after this period. The reflux condenser was then replaced with a distillation head. The acetic acid and residual ethyl acetate were distilled off under reduced pressure to produce the desired product.

Example IV - Reaction of the Modifier with the Oligomer The equipment used was a 250 ml pear-shaped uri flask equipped with a magnetic stir bar and a drying tube. The flask was charged with: (a) 25 grams of an oligomer, having a composition of 1: 2 (molar ratio) of HEA (monomer A) to EA (monomer B); (b) 50 ml of THF; Y (c) 12.2 grams of isocyanatoethyl methacrylate (ICEMA). 0.05 g of dibutyl tin dilaurate catalyst was added to this mixture at 25 ° C. The mixture was then stirred at 25 ° C for two days. An additional 0.45 g of the same catalyst was added and the mixture was heated in an oil bath to 50 ° C for 4 days. At this time, it was determined that all the isocyanate groups had been converted to urethane groups. The product was concentrated by removal of the volatile substances with a rotary evaporator. The product was characterized by the infrared spectroscope of the Fourier transformer (FTIR); nuclear magnetic resonance C-13 (NMR); the two-dimensional NMR, and the MALDI-MS. The glass transition temperature (Tg) and the viscosity of the liquid product were -73 ° C and 16,000 MPa-sec (cps, Brookfield viscometer at 25 ° C), respectively.

Example V - Reaction of the Modifier with the Oligomer The following are other examples. Reactions 1-4 were carried out in net form, and reactions 5-10 in toluene under reflux with azeotropic water removal. The reaction mixture also contained inhibitors: 1. 4-hydroxy-2,2,6,6-teramethylpiperidinyloxy (HTEMPO, 500 ppm); 2: butylated hydroxytoluene (BHT, 1000 ppm) / air; 3. HTEMPO (500 ppm); 4. HTEMPO (500 ppm); 5: BHT (1000 ppm / air; 6: hydroquinone (1000 ppm) / air; 7. HTEMPO (500 ppm); 8: HTEMPO (500 ppm); 9: HTEMPO (500 ppm); 10: HTEMPO (500 ppm).

Table 5 a Pl: 6.0 n-butyl acrylate / 2.5 glycidyl acrylate (molar ratio); Mw / Mn = 2245/1083; Dp = 8.5 P2: 5.6 n-butyl acrylate / 2.6-hydroxybutyl acrylate (molar ratio); Mw / Mn = 2130/1091; Dp = 8.0 P3: 4.8 n-butyl acrylate / 2.4-hydroxybutyl acrylate (molar ratio); Mw / Mn = 1965/969; Dp = 7.2 b. AA: acrylic acid; AOPA: acrylopropionic acid c. Cr: chromium 2-ethylhexanoate, 0.1% by weight based on the total weight of the reaction mixture, -100 ppm Cr.MSA: methanesulfonic acid; for operations 5, 6 and 7, 2 mole% of MSA, based on HBA in the oligomer were used. AM: Amberlyst 15 [Amberlyst is a registered trademark of Rohm and Haas Company] d.) Conversion of the functional group into the oligomer. e.) Conversion of the reactive part in modifier f.) 40% molar of concentration g.) Temperature of toluene at reflux h. ) Not measured These examples showed that the oligomers could react with the modifiers to form the products of this invention.

Example VI - UV curing An oligomer, either net or formulated, was applied to the surface of a substrate, using a wet film applicator to form a film with a thickness of 51 microns. The applicator used was an Eigh-Path Wet Film Applicator, from Paul N. Gardner Company, Inc. Substrates include glass, aluminum, and cold-rolled steel. The coated surfaces were then cured in air or nitrogen, with a RPC Model 1201 UV processor, equipped with medium pressure mercury arc lamps of 80 watts / cm, at a band speed of 6 to 30 meters per minute. The following table represents the typical energy / area at various band speeds, measured using a Compact Radiometer radiometer (UV Process Supply Inc.).

Table 6 The following Table 7 shows the results of the cure obtained with the net product, in the presence of 2% by weight of Darocure 1173, obtained from Ciba Specialty Chemicals.

Table 7 a.) determined by the ratio of the wet sample weight to the final dry sample weight in tetrahydrofuran (THF). b.). { (initial sample weight - final dry sample weight) / initial sample weight) x 100% in THF The following Table 8 shows the results of the curing with the product B2 in the presence of different amounts of the monomer TMPTA (and 2% by weight of Darocure 1173, obtained from Ciba Specialty Chemicals).

Table 8 * low nitrogen These examples show that the curable compositions, prepared according to the present invention, can be cured under a variety of conditions.

Claims (30)

R E I V I N D I C A C I O N S

1. A process for preparing a curable composition, which comprises: a.) Forming an oligomer, having a degree of polymerization in the range of 3 to 100, of the oligomerization of a mixture, which comprises a monomer A and a monomer B , under a first condition, in which monomer A has at least one functional group, which either is generated after oligomerization or is present in monomer A prior to oligomerization and remains substantially unreacted during oligomerization; the oligomer or has a first number of monomer units, incorporated in its backbone; and wherein the first condition comprises a temperature in the range of 150 to 650 ° C, a pressure in the range of 3 to 35 MPa, which is sufficient to maintain the mixture in a fluid state and a residence time at that temperature and pressure in the range of 0.1 second to 4 minutes; and b.) reacting a modifier, which has at least one reactive part, with the oligomer, through a reaction under a second condition, between the reactive part of the modifier and the functional group of monomer A incorporated in the oligomer, for producing the curable composition, wherein the modifier further comprises a curable group selected from the group consisting of a carbon-to-carbon double bond, a heterocyclic oxygen-containing group, and mixtures thereof, and this curable group remains outstanding in the curable composition and interlacing after the reaction.

2. The process of claim 1, wherein the monomer B is selected from the group consisting of: ethylene, propylene, C4 to C10 α-olefins, butadiene, isoprene, styrene, substituted premiere, vinyl ester, vinyl ether, silane vinyl, vinyl halide, acrylic acid, methacrylic acid, crotonic acid, alkyl acrylate ester, alkyl methacrylate ester, alkyl crotonate ester, acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, and mixtures thereof .

3. The process of claim 1, wherein the functional group is selected from the group consisting of a hydroxyl group, a carboxylic acid group, a halide, an oxirane group, an anhydride group, an ester, an alkoxysilyl group and a double bond from carbon to carbon.

4. The process of claim 2, wherein the monomer B is selected from the group consisting of: vinyl acetate, vinyl benzoate, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, acrylate n-butyl, sec acrylate -butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, methacrylate of sec. -butyl, 2-ethylhexyl methacrylate, 2-ethylhexyl croatonate, N, N-dimethylacrylamide, N, N-dimethylacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide, N, N-dimethylmethacrylamide, N , N-diethylmethylacrylamide, vinyl chloride, vinyl bromide, vinyl ethyl ether, vinyl n-propyl ether, vinyl n-butyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, -chloroethyl vinyl ether, vinyltrimethylsilane and their mixtures.

5. The process of claim 1, wherein the monomer A is selected from the group consisting of: allyl alcohol, allyl acetate, allyl propionate, allyl acrylate, allyl methacrylate, allyl crotonate, vinyl acrylate, vinyl methacrylate , vinyl crotonate, 1,3-butadiene, isoprene, glycidyl methacrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate , 4-hydroxybutyl methacrylate, maleic anhydride, itaconic anhydride, citraconic anhydride, vinyltrimethoxysilane, β-methacryloxy-propyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, allyltriethoxysilane, allyltrichlorosilane and mixtures thereof; and monomer B is selected from the group consisting of: acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid, methyl cinnamic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-methacrylate, -propyl, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec acrylate. -butyl, methacrylate sec. -butyl, and their mixtures.

6. The process of claim 1, wherein the modifier is selected from the group consisting of an ethylenically unsaturated acid, an ethylenically unsaturated ester, and mixtures thereof, and the functional group consists essentially of a hydroxyl group or an ester group.

7. The process of claim 1, wherein the modifier is selected from the group consisting of an ethylenically unsaturated carboxylic acid, and the functional group of monomer A is selected from the group consisting of a hydroxyl, an oxyranyl, a carbon double bond to carbon, and their mixtures.

8. The process of claim 1, wherein the modifier is selected from the group consisting of a hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid, and mixtures thereof, and the functional group of monomer A is selected from the group consisting of an anhydride, an alkoxysilyl, and mixtures thereof.

9. The process of claim 1, wherein the modifier is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, methyl acrylate, methyl methacrylate, methyl crotonate, ethyl acrylate, ethyl methacrylate, ethyl crotonate , n-propyl acrylate, n-propyl methacrylate, n-propyl crotonate, i-propyl acrylate, i-propyl methacrylate, i-propyl crotonate, n-butyl acrylate, n-butyl methacrylate, crotonate of n-butyl, and mixtures thereof, acryloyl chloride, methacryloyl chloride, crotonyl chloride, and mixtures thereof; and the monomer A is selected from the group consisting of the allyl alcohol, allyl acetate, allyl propionate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl crotonate, 3-hydroxypropyl acrylate, 3-methacrylate, and hydroxypropyl, 3-hydroxypropyl crotonate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxbutyl crotonate, and mixtures thereof.

10. The process of claim 1, wherein the modifier is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid, methyl cinnamic acid, and mixtures thereof; and monomer A is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 4-vinyl-cyclohexen-1, 2-epoxide, butadiene, isoprene, l-vinyl-4-cyclohexene, norbornadiene, and mixtures thereof.

11. The process of claim 1, wherein the modifier is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl crotonate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, crotonate 3-hydroxypropyl, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl crotonate, and mixtures thereof; and monomer A is selected from the group consisting of maleic anhydride, itaconic anhydride, citraconic anhydride, vinyltrichlorosilane, vinyltrimethoxysilane, vinyl crotonate, and mixtures thereof.

12. The process of claim 1, wherein the monomer A is selected from the group consisting of vinyl chloride, vinyl bromide, vinyl acetate, vinyl benzoate, vinylidene chloride, vinylidene fluoride, and mixtures thereof; and the modifier comprises a salt of a metal of an acid set up, where the metal is selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Ga, In, and mixtures thereof, and the saturated acid is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid, methyl cinnamic acid, and mixtures thereof; and wherein the second conditions further comprise the addition in an amount of 0 to 50 mole% of a phase transfer catalyst, based on the moles of the modifier.

13. The process of claim 1, wherein the second number of the functional group is produced after the oligomerization, and wherein the ratio of the second number of the functional group to the first number of monomer units incorporated into the oligomer backbone, is in the interval from 1: 100 to 1: 1.

14. The process of claim 1, wherein the functional group is present in monomer A and remains substantially unreacted during oligomerization, and wherein the molar ratio of monomer A to monomer B incorporated in the oligomer is in the range of 1. : 40 to 40: 1.

15. The process of claim 1, wherein monomer B comprises ethyl 4,4,4-trifluorocrotonate.

16. The process of claim 2, wherein the vinyl ether is selected from the group consisting of ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2- ethylhexyl vinyl ether, 2-chloroacetyl-vyl ether, and mixtures thereof, and the vinyl silane comprises vinyltrimethylsilane.

17. The process of claim 1, further comprising curing the curable composition by a method selected from the group consisting of the chemical generation of free radicals, electrochemical generation of free radicals, photochemical generation of free radicals, electron beams, electromagnetic irradiation selected from group consisting of ultraviolet radiation, visible light, X-ray and gamma irradiation, and combinations thereof, to produce a cured product of the radiation curable composition.

18. The process of claim 17, wherein the method is selected from the group consisting of ultraviolet irradiation, visible light, electron beams, and combinations thereof, and the curable composition further comprises an additive selected from the group consisting of one or more photoinitiators, one or more diluent monomers, and their mixtures.

19. A process for preparing a composition curable by electromagnetic irradiation, this process comprises: a.) Forming an oligomer of the oligomerization of a mixture, which comprises a monomer A and a monomer B, in which monomer A has at least one group functional, which either is generated after oligomerization or is present in monomer A prior to oligomerization and remains substantially unreacted during oligomerization; the monomer B is selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec acrylate. -butyl, methacrylate sec. - butyl, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and mixtures thereof; and b.) producing the composition curable by electromagnetic irradiation by reacting a modifier, having at least a reactive part with the oligomer, through a reaction between the reactive part of the modifier and the functional group of monomer A, which has been incorporated in the oligomer, wherein the modifier further comprises a carbon-to-carbon double bond, which remains suspended in the curable composition of electromagnetic radiation and interlaced with the irradiation after the reaction; c.) recovering the curable composition by electromagnetic irradiation; and d) subjecting the composition curable by electromagnetic irradiation to this electromagnetic irradiation, to produce a product cured by electromagnetic irradiation.

20. A composition curable by electromagnetic irradiation, comprising an oligomer having double bonds of carbon to carbon, interlaced by electromagnetic irradiation, suspended, in which the oligomer has a degree of polymerization in the range of 3 to 100, and is prepared by a oligomerization of a mixture, which comprises a monomer A and a monomer B, wherein monomer A has at least one functional group, which remains substantially unreacted during oligomerization, and monomer B is selected from the group consisting of acrylic acid , methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec acrylate -butyl, methacrylate sec. -butyl, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and mixtures thereof; and producing the composition curable by electromagnetic irradiation by the reaction of a modifier having at least one reactive part with the oligomer, through a reaction between the reactive part of the modifier and the functional group of the monomer A, which has been incorporated in the oligomer, wherein the modifier further comprises a carbon-to-carbon double bond, which remains suspended in the curable composition by electromagnetic irradiation and can be intertwined with this electromagnetic irradiation after the reaction.

21. The composition curable by electromagnetic irradiation, according to claims 19 or 20, further comprising an additive selected from the group consisting of one or more photoinitiators, one or more diluent monomers and their mixtures.

22. The curable composition of claims 1 to 18, wherein it is emulsified in a solvent consisting essentially of water, in the presence of a surfactant, to form a water-borne formulation.

23. A method for using the curable composition of claims 1 to 18, for coatings, films, paints, brands, adhesives, binders, inks and combinations thereof.

24. A method for using the water-bearing formulation of claim 22 for coatings, films, paints, brands, adhesives, binders, inks and combinations thereof.

25. A process for producing a composition curable by electromagnetic irradiation, this process comprises forming an oligomer having a degree of polymerization in the range of 3 to 100 from an oligomerization of a mixture, which comprises a monomer A and a monomer B, under a first condition, in which monomer A is selected from the group consisting of vinyl acrylate, vinyl methacrylate, vinyl crotonate and mixtures thereof; monomer B is selected from the group consisting of ethylene, propylene, C4 through C10 α-olefins, butadiene, isoprene, styrene, substituted styrene, vinyl ester, vinyl ether, vinyl silane, vinyl halide, acrylic acid, acid methacrylic, crotonic acid, alkyl acrylate ester, alkyl methacrylate ester, alkyl crotonate ester, acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, and mixtures thereof; : and in that the first condition comprises a temperature in the range of 150 to 650 ° C, a pressure in the range of 3 to 35 MPa, which is sufficient to maintain the mixture in a fluid state, and a residence time, at those temperatures and pressures, in the range of 0.1 second to 4 minutes.

26. A process for preparing a curable composition, comprising forming an oligomer, having a degree of polymerization in the range of 3 to 100, from the oligomerization of a mixture which comprises a monomer A and a monomer B, under a first condition, in which monomer A has at least one oxiranyl group, which is either generated after oligomerization or is present in monomer A, prior to oligomerization, and remains substantially unreacted during oligomerization; the oligomer has a first number of monomer units incorporated into its backbone; and wherein the first condition comprises a temperature in the range of 150 to 650 ° C, a pressure in the range of 3 to 35 MPa, which is sufficient to maintain the mixture in a fluid state, and a residence time to that temperatures and press in the range of 0.1 second up to 4 minutes.

27. The process of claim 26, wherein the monomer B is selected from the group consisting of ethylene, butadiene, isoprene, styrene, p-methylstyrene, methyl acrylate, methyl methacrylate, methyl crotonate, ethyl acrylate, ethyl methacrylate. , ethyl crotonate, n-propyl acrylate, n-propyl methacrylate, n-propyl crotonate, n-butyl acrylate, n-butyl methacrylate, n-butyl crotonate, 2-ethylhexyl acrylate, methacrylate 2 ethylhexyl, 2-ethylhexyl crotonate, vinyl acetate, vinyl ethyl ether, vinyl n-propyl ether, vinyl n-butyl ether, vinyltrimethylsilane, and mixtures thereof.

28. The process of claims 26 or 27, further comprising curing the. curable composition by a method selected from the group consisting of curing with acid, curing with bases, generation of acid by electromagnetic irradiation, selected from the group consisting of ultraviolet, visible light, X-ray and gamma irradiation, and their combinations, to produce a cured product from the radiation curable composition.

29. The composition curable by electromagnetic irradiation, of claims 19 or 20, wherein it is emulsified in n solvent, consisting essentially of water, in the presence of a surfactant, to form a water-bearing formulation.

30. A method for using the composition curable by electromagnetic irradiation, according to claim 29, for a coating, film, paint, marking, adhesive, binder, ink, and combinations thereof.