MXPA99011633A - 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 C. to 650 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 OF CONTINUOUS POLYMERIZATION AND PRODUCTS OF THIS The present invention relates to a continuous polymerization process and to products thereof. In particular, the present invention relates to a process of continuous polymerization at high temperature and at high pressure to produce oligomers. More particularly, the present invention relates to a process of continuous polymerization at high temperature and at high pressure to produce unsaturated and fully saturated final oligomers. "Oligomers", as used herein and in the appended claims, refers to polymers having a degree of polymerization ("dP") of less than 50. For a long time the art has sought an inexpensive way , efficient and healthy from the environmental point of view to produce, polymers with low molecular weight. However, the production of these low molecular weight polymers has proven difficult. One method to achieve polymers with low molecular weight is through the application of efficient chain transfer agents, but this approach has several disadvantages. First, this approach incorporates the structure of the chain transfer agent in the polymer chain. This may be undesirable since the structure will have an effect that will increase the properties of the polymer as the molecular weight decreases. Moreover, the chain transfer agents commonly employed are mercap- anes. These materials are expensive and have unpleasant odors related to their presence. Other common chain transfer agents are hypophosphites, bisulfites and alcohols. These are also added to the cost of the process, impart functionality to the polymer, can introduce salts into the product and may require a separation step of the product. Another way to decrease the molecular weight of the polymers is by increasing the amount of the initiator. This approach considerably increases the cost of production and can cause degradation of the polymer chain, and high levels of unreacted initiator remaining in the product. In addition, the high levels of the initiator can also cause high levels of salt products in the polymer mixture known to be detrimental to the performance of many applications. The same is true for chain-interrupting agents, for example sodium metabisulfite. Among the preferred free radical initiators for aqueous polymerization is hydrogen peroxide. It is relatively inexpensive, has little toxicity and does not produce harmful salt byproducts. However, hydrogen peroxide generally does not decompose efficiently at conventional polymerization temperatures and usually large quantities must be used to generate sufficient radicals to carry out the polymerization. It has also been tried as a method to control molecular weight high levels of metal ions, alone or together with high levels of the initiator. Such an approach is not suitable for certain products that can not tolerate contaminants of metal ions in the polymer product, for example pharmaceutical, medical and electronic applications. In addition, depending on the metal ions used, the product may discolor due to the presence of metal ions. U.S. Patents 4,680,352 and 4,684,054 present processes for preparing low molecular weight, terminally unsaturated oligomers, which employ metal chelate chain transfer agents to control molecular weight. These processes suffer from the same problems as processes that employ a high level of metal ions, as described above. Furthermore, since the methods employing the metal chelate chain transfer agents undergo ß-cleavage reactions, they are limited to producing oligomers having homometacrylate as the main elements. In European Polymer Journal, Volume 8, pages 321-328 (10972), Feit describes a multi-step synthesis technique for preparing terminally unsaturated oligomers and co-oligomers of vinyl monomers having electronegative groups. The process described in that document requires a base catalyzed addition of an ester of acetic acid derivative to an activated olefin, followed by the hydrolysis of an ester group, followed by a Mannich reaction to introduce a terminal double bond. This three step process is repeated to prepare a terminally unsaturated oligomer with an additional mer. This process suffers the disadvantage of being quite complex, expensive and long-lasting. U.S. Patent 5,710,227 presents a high temperature continuous polymerization process for preparing terminally unsaturated oligomers which are formed with acrylic acids and their salts, and acrylic acid and its salts with other ethylene glycol unsaturated monomers. The process of continuous polymerization at high temperature solves many problems related to previously known methods for preparing terminally unsaturated oligomers formed with acrylic acid. However, the pure form of many of the acrylic acid products are solid and, therefore, require the vision of a solvent to handle and use the products. U.S. Patent 4,356,288 prepares the preparation of terminally unsaturated oligomers formed with acrylic acid esters having a degree of polymerization of about 6-30 by an anionic polymerization reaction carried out in the presence of a catalytic amount of an alkoxide anion. The method is relatively complex. Since the method is inhibited by the presence of moisture (decreasing the yield and uniformity of the final product), it is not a viable commercial process. In Chemical Engineering at Supercritical Fluid Conditions, pages 515-533 (1983), Metzger et al. dimerization and trimerization of methyl acrylate in benzene at a pressure of 200 and at temperatures of 340-240 ° C in a flow reactor with a residence time of 5 minutes. The present invention seeks to overcome the problems related to previously known methods for preparing oligomers by providing a polymerization process that is not limited to the formation of oligomers having only a homometacrylate backbone or an acid-containing monomer residue backbone carboxylic and that does not require water or another solvent for the manufacture or use of the oligomer. The present invention also provides an oligomer free of contaminants of metal, salt and surfactant, which, given its purity and composition, is not sensitive to waste or discolour and is in the liquid state when it is pure. Declaration of the Invention The invention is directed to a continuous process for preparing terminally unsaturated and fully saturated oligomers not containing, as polymerized units, carboxylic acid containing monomers, which includes the steps of: (1) forming a reaction mixture , substantially free of carboxylic acid monomers and their salts, containing: (i) from 0.5 to 99.95% by weight of the reaction mixture of at least one unsaturated ethylene glycol monomer; (ii) from 0.05 to 25% by weight, based on the weight of the monomer, of at least one free radical initiator; and (2) passing the reaction mixture continuously through a hot zone where the reaction mixture is maintained at a temperature of at least 150 ° C and at a pressure of at least 30 bars from 0.1 seconds to 4 minutes to form terminally unsaturated oligomers. In addition, the invention is directed to a process for preparing completely unsaturated oligomers that includes the additional step of hydrogenating the terminally unsaturated oligomer. The invention is also directed to the process for forming vinyl acetate oligomers and vinyl alcohol oligomers. The process of the invention is useful for preparing oligomers with the formula: Z, wherein A, A1 and A2 independently selected from -H; straight or branched chain alkyl? C5o, optionally substituted with a group Y; straight or branched chain alkenyl C2-C5o containing 1-5 double bonds, optionally substituted with 1-2 Y groups; cycloalkyl with C5-Cs, cycloalkenyl with C5-C8; phenyl, (CH2) m-phenyl, 1- or 2-naphthyl; -NH (C = 0) NH2, -NH (C = O) NHR », -CHaCnFan + i, -CH2CH2CnF2n + ?, -CH (CF3) 2? -CH3CnF2nH, -CH2 CHaC "F2nH; -P (= 0) (ORi) 3; -S (= 0) 2 (ORi); .s (= 0) 2Ry independently selected from -H, -F, Cl, -Br, Rl; E1 and E2 independently selected from -H; G1, G2 independently selected from -H, -CH3, - (CH2) mC02R ?, -F, -Cl, -Br, -I; M1, M2 independently selected from -H, -C = N, - (C = 0) 0R1, -F, -Cl, -Br, -I; straight or branched chain alkyl with C? -C8, -OR3, residue from the decomposition of the radical of the azo initiators "(azonitrile, azoamidine, cyclic azoamidine, azoamide, azoalkyl classes); Example 10 -C (R4) 2G = N; straight or branched chain alkyl with C? -C50, straight or branched chain alkenyl C2-Cso containing 1-5 double links; cycloalkyl with Cs-C8, cycloalkenyl with C ^ -Cs; phenyl, (CH 2) m-phenyl, 1- or 2-naphthyl, 20 -4-benzoylphenyl (wherein any phenyl group can be substituted with up to 2 R 2), anthracenyl, anthracenylmethyl; - (CH2> mO (C = O) Ri, - (CH2) m (C = O) ORi; 25 - (CHa C-CRi; -CCH2) m (C = O) NH2, -CH2) m < C = O) NHRi, - (CH2) m (C «0) NH (Ri) 2; -CH2) mN < Ri.}. 2, - (CH2) mNH3 (+) (->; <CH? MOW- - (CH2CH2?) MRy - (CH2CH (CH3) O) B1R1) -2-tetrah.yd.rofuranyl; - (CH2) mN = C = 0; -CH2CnF2D +? »-CH2CH2C11F2" +? Í -CH (CF3) 2, -CH2CAH, or /? -CCH2) m HC CH2 i linear alkanes containing 1-5 epoxy groups derived from vegetable (poly) unsaturated oils; - (CH2) pOH, - (CHaCHsOVH, - [OH2CI? (CHj) 0] mH; 10 -. {CIÍ.) MSi (ORi) 3, - (CH2) 8Si (Ri) (OR >, - ( CH2) raSi (R ») 2? Ri, - (CHa SiíR '; independently selected from straight or branched chain alkyl Ci-Cs wherein (R1) 2 can constitute a cycloalkyl group with C5-C8; phenyl, -CH2phenyl; 20 R straight or branched chain alkyl with C? ~ C6, straight or branched chain alkoxy C? -C6, -CHO, - (C = 0) 0R1, -N (RX) 2, -N02, - (C = 0) N (R1) 2, -CF3 / - (C = 0) ORx, -F, -Cl, -Br, -I; 25H, straight or branched chain alkyl C? -C8, -R1 (C = 0), -R1 (C = 0) 0; R, 41 = straight chain alkyl C? -C? 8, C5-C8 cycloalkyl wherein the two adjacent R4 groups can form a 5-8 membered ring, straight or branched chain C? ~C alkyl groups substituted with alkoxy C? -C; X_) = -F (-), -Cl (-), -Br (-), -I (-), - HS04 (-), -H2P03 (-); Y = -OH, -F, -Cl, -Br, -I, -NH2, - N (R1) 2; m = 1-8 n '= 1-18 p = 2-8 x = 0-49 y = 0-49 z = 0-49 x + y + z < 49. The invention is also directed to a mixture containing: (1) about 50 to 90% by weight, based on the weight of the mixture, of a first oligomer having the terminal unsaturation of the formula (I), where at least E1 and E2 is a final group with formula: and wherein only one between E1 and E2 is a final group of formula (II) wherein the final group is independently selected from H, (2) about 10 to 50% by weight, based on the weight of the mixture, of a second oligomer that does not have the terminal unsaturation of the formula (I), wherein E1 and E2 are independently selected from DETAILED DESCRIPTION OF THE INVENTION As used herein, the term "methacrylate" refers to methacrylate and acrylate, the term "methacrylic" refers to methacrylic and acrylic and the term "methacrylamide" refers to methacrylamide and acrylamide. As used in the following document, the term "substantially free" means less than 0.5% by weight. As used herein, the term "environmental conditions" means at a temperature of 20 ° C-40 ° C and at a pressure of 1 bar. As used in this document, the term "homo-oligomer" means an oligomer that contains the same monomer units and the term "co-oligomer" means an oligomer that contains at least two different monomer units. As used herein, the term "pure" means a composition that contains only the oligomer and is substantially free of solvent and other additives. As used herein, the phrase "monomers containing carboxylic acid and its salts" means unsaturated monoethylene glycol monocarboxylic acids, and the alkali metal, alkaline earth metal and ammonium metal salts thereof, and unsaturated monoethylene glycol dicarboxylic acids, and the alkali metal, ferrous alkaline and ammonium metal salts thereof, and the anhydrides of the cis-dicarboxylic acids. The first step of the process of the invention is to form a reaction mixture, substantially free of monomers containing carboxylic acid and its salts, which contains: (a) from 0.5 to 99.95% by weight of the reaction mixture of less an unsaturated ethylene glycol monomer; (b) from 0.05 to 25% by weight, based on the weight of the unsaturated ethylene glycol monomer, of at least one free radical initiator. Preferably, the reaction mixture contains from 10% to 99.9% by weight, and more preferably, from 50% to 98% by weight, based on the weight of the reaction mixture, which at least one unsaturated ethylene glycol monomer . Preferably, the reaction mixture contains from 0.1% to 5% by weight, and more preferably from 1% to 2% by weight, based on the weight of the unsaturated ethylene glycol monomer, of at least one free radical initiator. The process of the invention is suitable for polymerizing any unsaturated ethylene glycol monomer, except monomers containing carboxylic acid and their salts. Suitable monomers include, but are not limited to, n-alkyl methacrylates, for example methyl acrylate, butyl methacrylate, octadecyl acrylate; branched alkyl methacrylates, for example isopropyl methacrylate, 2-ethyl hexyl acrylate, isobornyl methacrylate; cycloalkyl methacrylates, for example, cyclopentyl methyl acrylate, cyclohexyl methacrylate; straight or branched chain haloalkylmethacrylates, for example 2, 2, 2-trifluoroethyl acrylate, hexafluoroisopropyl methacrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl acrylate; aromatic alkyl methacrylates, for example, benzyl acrylate, 4-chlorophenethyl methacrylate; aromatic methacrylates, for example, phenyl acrylate, 4-benzoyl phenyl acrylate; hydroxyalkylmethacrylates, for example, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate; heterocyclyl methacrylates, for example, 3-oxazolidinyl ethyl methacrylate, N-ethyl-ethylene ureido methacrylate; aminoalkyl methacrylates, for example, N, N-dimethyl aminoethyl acrylate and acid salts of 2-aminoethyl acrylate, N, N-diethyl aminopropyl methacrylate; methacrylates containing ether, for example, ethoxyethoxyethyl acrylate, 2-tetrahydrofuranyl acrylate, ethyl ether of a polyalkoxylated ester of methacrylic acid; methacrylates containing silicone, for example, trimethoxysilylpropyl acrylate, diethoxymethylsilylpropyl methacrylate, isopropoxydimethylsilylpropyl acrylate; methacrylamides, for example, N-methyl acrylamide, N, N-dimethylaminopropyl methacrylamide; methacrylates containing epoxide, for example, glycidyl acrylate, methacrylates derived from partially or fully epoxidized polyunsaturated vegetable oils; unsaturated alkyl methacrylates, for example, vinyl acrylate, allyl methacrylate, 2,4-hexadienyl methacrylate; methacrylate ethers derived from polyunsaturated vegetable oils; terminal alkenes, for example, ethylene, 1-hexene, 3-vinyl cyclohexene; aralkenes, for example, styrene, 4-methyl styrene, α-methyl styrene, 4-methoxystyrene, 4-benzoyl styrene, 4-N, N-dimethylaminostyrene; heterocyclic alkenes, for example, 2, -3, or 4-vinyl pyridines and N-vinyl imidazole; dienes, for example, butadiene, isoprene, vinylidene chloride, vinyl fluoride; vinyl alures, for example vinyl chloride, tetrafluoroethylene; vinyl esters, for example vinyl acetate, vinyl benzoate; vinyl ketones, for example methyl vinyl ketone; aldehyde containing the vinyl functionality, for example, methacrolein and its acetal derivatives; epoxyalkenes, for example, 3, 4-epoxybut-1-ene; vinyl monomers, for example, methacrylonitrile, N-vinyl formamide, N-vinyl acetamide, fumaronitrile; vinylsilanes and alkoxyvinylsilanes, for example, vinyltrimethylsilane, vinyltrimethoxy silane, vinyldiethoxymethylsilane; unsaturated dienes, for example dimethylmaleate, dibuylfumarate, diethyl itaconate; functional methacrylates, for example, isocyanatoethyl methacrylate, acryloylchloride, acetoxylethoxyethyl methacrylate. Among the preferred ethylene glycol unsaturated monomers are those monomers whose pure homooligomer with a degree of polymerization of about 5 to about 10 is liquid at ambient conditions. Suitable initiators for carrying out the process of the invention are any free radical initiators, including, but not limited to, hydrogen peroxide, certain alkyl hydroperoxides, dialkyl peroxides, peresters, percarbonates, persulfates, peracids, oxygen, peroxides of ketone, azo initiators and combinations of these. Specific examples of some suitable initiators are hydrogen peroxide, oxygen, t-butyl hydroperoxide, tertiary butyl peroxide, amylothermal hydroperoxide, methylethyl ketone peroxide, and combinations thereof.

The monomers can be polymerized in the form of diluted solutions, although the process does not require solvent, nor is the use of these preferred. The reaction mixture may contain one or more solvents at a level of 0% to 99.5% by weight of the reaction mixture, preferably 30% to 97% by weight of the reaction mixture, and more preferably 30% by weight. % to 97% by weight of the reaction mixture. As the relative amount of one or more solvents in the reaction mixture decreases, particularly less than 60%, the molecular weight and polydispersity of the resulting oligomer mixture increases. Solvents suitable for the process of the present invention are capable of dissolving one or more monomers, especially under the supercritical fluid conditions of the process, and the monomers formed therefrom. Suitable solvents for the present invention include, for example, ethers, for example tetrahydrofuran, ketones such as acetone.; esters, for example, ethyl acetate; alcohols, for example, methyl alcohol and butyl alcohol; alkanes, for example, hexane and heptane; aromatic hydrocarbons, for example, benzene, toluene and xylene; supercritical fluids, for example carbon dioxide; Water; and mixtures of these. Supercritical fluids, for example, carbon dioxide, are particularly useful because the solvent can be easily separated from the product and can be recycled. In the second step of the process of the present invention, the reaction mixture is continuously passed through a hot zone, where the reaction mixture is maintained at a temperature of at least 150 ° C under high pressure. Once the reaction mixture is formed, it is preferable to make the passing reaction mixture reach the polymerization temperature as fast as possible. Preferably, the reaction mixture reaches the polymerization temperature within 2 minutes, more preferably within 1 minute, more preferably within 30 seconds. Before reaching the reaction temperature, the reaction mixture can be at any suitable temperature, preferably at a temperature ranging from room temperature to 450 ° C, more preferably from a temperature ranging from room temperature to 60 ° C. ° C up to 400 ° C. the oligomerization is carried out at a temperature of at least 150 ° C, and is preferably conducted at a temperature that is in the range of 200 ° C to 500 ° C, and more preferably at a temperature that is in the range of 275 ° C. C at 450 ° C. at temperatures below 150 ° C, the molecular weight of the oligomer increases and the relative amount of the derived products increases, particularly of the non-terminally unsaturated compounds. The oligomerization at high temperatures of the process of the invention is rapid. Therefore, the reaction mixture can be maintained at the polymerization temperature from 0.1 seconds to 4 minutes, preferably from 0.5 seconds to 2 minutes, more preferably from 1 second to 1 minute. Under prolonged periods of time in which the reaction mixture is exposed to the polymerization temperature, the yield of the terminally terminated oligomer decreases. However, it has been found that prolonged periods at the polymerization temperature have little effect on both the conversion of the monomer and the molecular weight of the products formed. The elevated temperatures of the polymerization require that the polymerization reactor be equipped to operate at an elevated pressure of at least 30 bars to maintain the contents of the reactor in the form of a fluid at the temperature of the reaction. In general, it is preferred to conduct the polymerization from 70 bars to 350 bars, and more preferably from 200 bars to 300 bars. In the process of the present invention, the unsaturated ethylene glycol monomers, the initiator and, optionally, the solvent combine to form a reaction mixture. The order of combination of the components of the reaction mixture is not fundamental to the process of the present invention. In one embodiment of the present invention, it may be desirable to use one or more solvents, to heat the solvent or solvents at an elevated temperature, and to add one or more monomers and at least one initiator to the hot solvent to form the mixture of the reaction. It is preferred to add the initiator at the end. The reaction mixture can be formed at a lower temperature, equal to or higher than the oligomerization temperature. In one form of the embodiment of the invention, it may be desirable to add an additional amount of solvent to the oligomer product while the oligomer is at an elevated temperature to maintain the desirable fluidity and viscosity properties of the oligomer product. Suitable reactors for making use in the process of the invention include tubular reactors having no moving parts and having a cross-sectional shape that allows continuous and constant flow and which can operate at elevated temperatures and pressures. Said reactors are typically manufactured with inert materials, for example stainless steel or titanium. The reactor can be any length and any dimension in cross section that allows effective control of temperature and pressure.

Depending on the final application of the oligomeric products of the invention, the reaction mixture may optionally con metal ions, for example copper, nickel or iron or combinations of both. However, their presence is not preferred. In general, the process of the invention produces a relative conversion of the monomers in the oligomer product from 10% to more than 95% relative to the initial amount of one of the monomers present in the reaction mixture. If residual monomer levels in the oligomer mixture are unacceptably high for a particular application, their levels can be lowered by any of several techniques known to those skilled in the art, including rotary evaporation, distillation and vacuum distillation. Preferably, any residual monomer that may be present in the oligomer mixture is distilled or "separated" and recycled for later use. The process of the present invention produces oligomers that have low molecular weights and reduced polydispersities. In addition, the process embodiments produce products that do not require the removal of organic solvents (if none were used in the process) and are not coinated with high salt levels. The process of the present invention can be applied to produce oligomers having average molecular weights less than 5,000, preferably less than 3,000, and more preferably from 200 to 1,000. The process of the invention may con an optional third step wherein the terminal unsaturation of the terminally unsaturated oligomers is removed by hydrogenation under conditions known to those skilled in the art, with or without solvent. Preferably, the hydrogenation can be carried out using a variety of hydrogenation catalysts in an alkali metal salt support. Among the preferred metallic catalysts are those comprising metals selected from groups 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 of the Periodic Table of the Elements as it appears published in Chemical and Engineering News 36 (5), 27, 1985, it is preferably present in the reaction in a ratio of 0.01 to 5.0 and preferably 0.02 to 2.0 grams of catalyst per gram of unsaturated oligomer. The degree of hydrogenation is determined from proton NMR measurements at 25 ° C using oligomer solutions in CDC13 with TMS as internal reference. After hydrogenation the resonances associated with the olefinic protons are converted into aliphatic protons. Thus, the efficiency of the saturation can be measured by analyzing the resonances of remaining olefinic protons.

The process of the invention is useful for preparing oligomers with the formula: Zi where A, A1 and? = selected independently of -H; straight or branched chain alkyl C1-C50, optionally substituted with a group Y; straight or branched chain alkenyl C2-Cso coning 1-5 double bonds, optionally substituted with 1-2 Y groups; cycloalkyl with C5-C8, cycloalkenyl with C5-C8; phenyl, (CH2) m-phenyl, 1- or 2-naphthyl; -NH (C = 0) NH2, -NH (C = 0) NHRi, -CHaCn za *! -CH2CH2C "F2n + ?. -CH (CF3) 2) -CHaCnF2nH, -CH- ,. CH2CnF2nH; -P (= 0) (ORi) s; -S (= 0) 2 (OR; -S (= 0) 2R *; A3, A4 independently selected from -H, -F, Cl, -10 Br, Rl; E1 and E2 independently selected from -H; G2 independently selected from -H, -CH3; twenty - . 20 - (CHz ^ COzRi, -F, -Cl, -Br, -I, M1, M2 independently selected from -H, -C = N, - (OO) OR1, -F, -Cl, -Br, -I; Straight or branched chain alkyl with Ci-Cß, -OR, residue from the decomposition of the radical of the azo initiators (azonitrile, azoamidine, cyclic azoamidine, azoamide, azoalkyl classes), for example -C (R4) 2C = N; R straight or branched chain alkyl with C1-C50, straight chain alkenyl or branched C2-Cso coning 1-5 double bonds; cycloalkyl with C5 ~ Cs, cycloalkenyl with C5-C8; phenyl, (CH2) m-phenyl, 1- or 2-naphthyl, -4-benzoylphenyl (wherein any phenyl group can be substituted with up to 2 R2), anthracenyl, anthracenylmethyl; twenty -. { CH2) mN (R *) 25 - (CH2) mNH3 < + «W; - (CH2) mORi, - (CH2CH2O) mR1, - (CH2CH (CH3) 0) mR ?, -2-tetrahy drofuranyl; - (CHa) JSM 0; -CH2Cn 2a +? S -CH2CH2CnF2n + ?, -CH (CF3) 2, -CH2CaF2aH, 25 O, / \ - (CH2) m HC- ~ CH2 and linear alkanes containing 1-5 epoxy groups derived from vegetable oils (poly) unsaturated; - (CHa) POH, - (CH2CH20) "1H? ~ [CH2CH (CH3) 01mH; - (CB.¿-) mSi (?, - (CH2) Si (Rn (OR? H, - (CH2.} .mSi (Ri) 2? Ri, - (CH2.} .mSi (Ri.) 3; independently selected from C?-C8 straight or branched chain alkyl wherein (R 1) 2 can constitute a C5-C8 cycloalkyl group; phenyl, -CH2phenyl; straight or branched chain alkyl with C? -Ce, straight or branched chain alkoxy C? -C6, -CHO, - (C = 0) 0R1, -N (RX) 2, -N02, - (C = 0) N (RX) 2, -CF3, - (C = 0) OR1, -F, -Cl, -Br, -I; ? -H, straight or branched chain alkyl C? -C8, -R1 (C = 0), -Rx (C = 0) 0; = straight chain alkyl C? -C? 8, Cs-C8 cycloalkyl wherein the two adjacent R4 groups can form a 5-8 membered ring, C? -C8 straight or branched chain alkyl groups substituted with alkoxy C! - C4; X (-) - F (-), -Cl (-), -Br (-), -I (-), - HS04 (-), -H2P03 (-); Y -OH, -F, -Cl, -Br, -I, -NH2, -N (RI) 2; m 1-8 n 1-18 P 2-8 x 0-49 and 0-49 z 0-49 x + y + z < 49. It is understood that the residues of the monomers, Zl f Z2 and Z3, which are present in the oligomers of the formula (I) above, can be arranged randomly to form alternating, random or block polymer structures. It is also understood that not only homo-oligomers and co-oligomers are contemplated, but oligomers formed from two different types of monomers, for example, terpolymers below molecular weight or "ter-oligomers". In the broadest sense, it is understood that in the oligomer in which there are 49 possible monomer residues (whether of structure Zi, Z2 and Z3) the monomers are each independently selected, whereby it would be possible to form an oligomer from of 49 different monomers. The process of the present invention is useful for producing a mixture of oligomers containing: (1) about 50 to 90% by weight, based on the weight of the mixture, of a first oligomer having the terminal unsaturation of the formula ( I), where at least E1 and E2 is a final group with formula: and wherein only one between E1 and E2 is a final group of formula (II) wherein the final group is independently selected from H, about 10 to 50% by weight, based on the weight of the mixture, of a second oligomer that does not have the terminal unsaturation of the formula (I), wherein E1 and E2 are independently selected from The mixture may optionally contain an oligomer formed by a chain-chain termination reaction. The terminal unsaturation can be detected and measured by conventional techniques, including H NMR spectroscopy, 13C NMR spectroscopy, and titration by bromine. The final groups can be identified through conventional techniques, including MALDI-MS. The terminally unsaturated oligomers, the fully saturated oligomers and the mixtures of the invention can be delivered pure and flow at ambient conditions. The consistency of the products varies from a thin fluid similar to water to a viscous fluid similar to molasses. Furthermore, they do not require the use of water or other solvents in the preparation or use and are substantially free of contaminants, including salts, surfactants, metals and the like.

The oligomers of the invention can be used pure, provided in solvent or emulsified in water with at least one surfactant. The oligomer emulsified in water is preferred if the pure form of the oligomer is too viscous to be used in an application. Conventional suitable surfactants include anionic, cationic, nonionic, amphoteric surfactants and mixtures thereof. The surfactant may be added at a level of at least 0.1% solids based on the weight of the oligomer. The emulsified composition can be prepared by mixing at least one surfactant, at least one oligomer, water and mixing vigorously. Other minor components, for example a wetting agent, are added to the emulsified composition. Alternatively, the emulsified composition can be prepared by adding the surfactant to the reaction mixture containing the unsaturated ethylene glycol monomer and the initiator prior to oligomerization. The oligomers of the invention are useful in many applications, including, for example, in binders and additives (surfactants, emulsifiers, rheology modifiers) for architectural coatings (paints, primers, lacquers, varnishes, markers, EIFS); in industrial coatings (including automotive finishes, metallic finishes, inks for printing and resin).

Products for construction (wood coatings and binders, shoe parts, sealants, modifiers and coatings for concrete, impregnants, varnishes) in coatings and additives for paper, textiles and non-woven fabrics; in adhesives; in chemical compounds for leather; in chemical formulation compounds (including detergents, dispersants, water treatment, scale inhibitors, suspension additives); in plastics and plastic additives (plasticizers, elements for processing); in rubber and rubber additives (plasticizers, elements for processing); in biosides and adjuvants; in chemical compounds and agricultural adjuvants; in chemical compounds for electronics; in ion exchange resins (adsorbents and adsorbents); in oil additives; in solvents; the lubricants and hydraulic fluids; and similar. Examples Equipment and General Procedures A 10-foot-long piece of stainless steel pipe with an inner diameter of 1/16 of an inch and a wall thickness of 0.050 of an inch was connected to one end of a high-pressure pump (Hewlett Packard Model HP 1050 TI) and at the other end to a back pressure control device. Between the two ends, the tube section was wound around a metal mandrel with a toroidal shape. The mandrel was placed on the main coil of a transformer in such a way that the coils of the pipe and the mandrel worked as secondary coils of the transformer. The pipe coils were additionally equipped with one end of a temperature probe. The other end of the temperature probe was connected to the temperature control device. The temperature control device regulated the current supplied to the main coil of the transformer, which had the effect of regulating the heat of the inductance imparted to the wound steel tube. A reaction mixture was prepared by mixing solvent (if present), monomers, comonomers (if present) and initiator. The nitrogen was bubbled through the mixture while stirring. In solvent-free conditions, the initiator and monomers / comonomers were fed separately into the reactor. The solvent was pumped through the tube through the high pressure pump at a rate of 0.05 to 10 milliliters per minute ("ml / min"). The pressure was maintained at a level of 200 bars at 350 bars. Current was supplied to the transformer main coil to increase the temperature inside the tube to the desired polymerization temperature. After about 15 minutes, the solvent in which it was pumped through the tube was replaced by the reaction mixture that was pumped continuously through the tube at the same speed, temperature and pressure, after allowing a time lapse suitable for the solvent to be cleaned from the tube, the product was collected in the form of an effluent in the back pressure control device. When the reaction mixture almost disappeared, solvent was pumped through the tube at the same speed, pressure and temperature as the reaction mixture. The solvent and the residual monomer were removed with a rotary evaporator. The terminal unsaturation was detected and measured both through 1 H NMR spectroscopy and 13 C NMR spectroscopy, the final groups were identified through MALDI-MS. Examples 1-103 are oligomerizations carried out in accordance with the general procedure described above. The conditions of the reaction and the final properties of the oligomers are shown in Table 1. m OO Abbreviations used in the table: EA = ethyl acrylate; BA = butyl acrylate; MA = methyl acrylate; LA = lauryl acrylate; VAc = vinyl acetate; MMA = methyl methacrylate; VTMO = vinyltrimethoxysilane; HEA = hydroxyethyl acrylate; GA = glycidyl acrylate; dTBP = di-t-butyl peroxide; tBHP = tert-butylhydroperoxide; H202 = hydrogen peroxide 1 Based on the weight of the monomer 2 Percent of the weight of the solvent based on the total weight of the composition 3 Conversion was measured as a function of the solid elements of the product, and was also determined through residual monomer analysis using high pressure liquid chromatography or gas chromatography 4Measured by gel penetration chromatography (GPC) by applying a standard of oligomeric butyl acrylate or oligomeric ethyl acrylate, unless specifically stated otherwise. Degree of polymerization measured through 1 H NMR unless specifically noted otherwise. 6Viscosity measured with a Brookfield viscometer at 25 ° C. 7 Measurement by differential scanning calorimetry at a rate of 20 ° C / minute unless specifically stated otherwise The pure oligomeric product was subsequently added to the methanol and boiled with a 1% sodium hydroxide solution until precipitated the oligomeric vinyl alcohol. After the solvent was removed, the hydrolysis degree was determined in > 90% with Mw / Mn = 2850/990 (calculated from oligomeric vinyl acetate). Tg was measured at 40 ° C (conventional oligomeric vinyl acetate has a Tg of 80 ° C). Oligomeric vinyl acetate dissolves easily to > 40 ° solids in water with gentle agitation (conventional oligomeric vinyl acetate requires prolonged heating to dissolve). 9 Estimated from the Tg and a published graph of the Tg compared to d. [Haggard et al., Prog. Org. Coa tings, Volume 12, No. 1, page 19 (1984)] "molar ratio 50:50 ^ Determined using the pMMA standards and converted to oBA standards using the following equations (assuming linearity and accuracy at higher molecular weights) MW (OBA std) = 432 + 0.447 Mw (pMMA std) n (oBA std) = 169 + 0.713 Mn (pMMA std) All the examples of the invention were liquids, and varied from low to high viscosity, when pure were provided, without If the reaction of the mixture contained the optional solvent during the manufacturing process, although only a few embodiments of the invention have been shown and described in the present document, it will be apparent to those skilled in the art that various modifications can be made. and changes in the process and compositions without departing from the scope of the present invention.

Claims (22)

1. A process for forming oligomers, comprising the steps of: (1) forming a reaction mixture, substantially free of carboxylic acid monomers and their salts, comprising: (i) from 0.5 to 99.95% by weight of the mixture of the reaction of at least one unsaturated ethylene glycol monomer; (ii) from 0.05 to 25% by weight, based on the weight of the monomer, of at least one free radical initiator; and (2) passing the reaction mixture continuously through a hot zone where the reaction mixture is maintained at a temperature of at least 150 ° C and at a pressure of at least 30 bars from 0.1 seconds to 4 minutes to form terminally unsaturated oligomers.

2. A process for forming oligomers having a degree of polymerization of at least 4, comprising the steps of: (1) forming a reaction mixture, substantially free of monomers containing carboxylic acid and its salts, comprising: (i) from 0.5 to 99.95% by weight of the reaction mixture of at least one unsaturated ethylene glycol monomer; And (ii) from 0.05 to 25% by weight, based on the weight of the monomer, of at least one free radical initiator; And (2) passing the reaction mixture continuously through a hot zone where the reaction mixture is maintained at a temperature of at least 150 ° C and at a pressure of at least 30 bars from 0.1 seconds to 4 minutes to form terminally unsaturated oligomers.

The process of claims 1 or 2, wherein step (2) is performed in a tubular reactor that has no moving parts.

4. The process of claims 1 or 2, wherein the unsaturated ethylene glycol monomer is at least one monomer selected from the group consisting of n-alkyl methacrylates, branched alkyl methacrylates, cycloalkyl methacrylates, straight or branched chain alkyl methacrylates, aromatic alkyl methacrylates. , aromatic methacrylates, hydroxyalkyl methacrylates, heterocyclyl methacrylates, aminoalkyl methacrylates, methacrylates containing ether, methacrylates containing silicone, methacrylamides, methacrylates containing epoxides, unsaturated alkyl methacrylates, methacrylate esters derived from polyunsaturated vegetable oils, terminal alkenes, aralkenes, alkenes heterocyclyl, dienes, vinyl halides, vinyl esters, vinyl ketones, vinyl functionality containing aldehyde, epoxyalkenes, vinyl monomers, vinylsilanes, alkoxyvinylsilanes, unsaturated diesters and functional methacrylates.

The process of claims 1 6 2, wherein the reaction mixture comprises at least two different unsaturated ethylene glycol monomers.

The process of claims 1 or 2, wherein the reaction mixture comprises at least three different ethylene glycol unsaturated monomers.

The process of claim 2, wherein the reaction mixture further comprises from 0% to 99.5 of solvent.

The process of claim 7, wherein the solvent is at least one solvent selected from a group consisting of tetrahydrofuran, acetone, ethyl acetate, methyl alcohol, butyl acrylate, hexane, heptane, benzene, toluene, xylene, carbon dioxide, water and mixtures of these.

The process of claims 1 or 2, further comprising the step of: (3) hydrogenating the terminally unsaturated oligomers.

The process of claims 1 or 2, wherein the hot zone is maintained at a temperature of 200 ° C to 500 ° C.

The process of claims 1 or 2, wherein the hot zone is maintained at a temperature of 275 ° C to 450 ° C.

12. The process of claims 1 or 2, wherein the hot zone is maintained at a pressure of 70 bars at 350 bars.

13. The process of claims 1 or 2, wherein the hot zone is maintained at a pressure of 200 bars at 300 bars.

14. The process of claims 1 or 2, where the reaction mixture is maintained in the hot zone from 0.5 seconds to 2 minutes.

15. The process of claims 1 or 2, wherein the reaction mixture is maintained in the hot zone from 1 second to 1 minute.

16. A process for forming vinyl acetate oligomers, comprising the steps of: (1) forming a reaction mixture, substantially free of carboxylic acid monomers and their salts, comprising: (i) from 0.5 to 99.95% by weight, based on the weight of vinyl acetate; and (ii) from 0-05 to 25% by weight, based on the weight of the vinyl acetate, of at least one free radical initiator; and (2) passing the reaction mixture continuously through a hot zone where the reaction mixture is maintained at a temperature of at least 150 ° C and at a pressure of at least 30 bars from 0.1 seconds to 4 minutes to form vinyl acetate oligomers.

17. A process for forming vinyl alcohol oligomers, comprising the steps of: (1) forming a reaction mixture, substantially free of carboxylic acid monomers and their salts, comprising: (i) from 0.5 to 99.95% by weight, based on the weight of vinyl acetate; and (ii) from 0.05 to 25% by weight, based on the weight of the vinyl acetate, of at least one free radical initiator; and (2) passing the reaction mixture continuously through a hot zone where the reaction mixture is maintained at a temperature of at least 150 ° C and at a pressure of at least 30 bars from 0.1 seconds to 4 minutes to form vinyl acetate oligomers. (3) hydrolyze the vinyl acetate oligomers in the presence of a catalyst to form oligomers of vinyl alcohol.

18. A process for forming vinyl alcohol oligomers, comprising the steps of: (1) forming a reaction mixture, substantially free of carboxylic acid monomers and their salts, comprising: (i) from 0.5 to 99.95% by weight, based on the weight of vinyl acetate; and (ii) from 0.05 to 25% by weight, based on the weight of the vinyl acetate, of at least one free radical initiator; and (2) passing the reaction mixture continuously through a hot zone where the reaction mixture is maintained at a temperature of at least 150 ° C and at a pressure of at least 30 bars from 0.1 seconds to 4 minutes to form vinyl acetate oligomers. (3) transesterify the vinyl acetate oligomers with an alcohol in the presence of a catalyst to form oligomers of vinyl alcohol.

19. The process of claims 16-18 wherein step (2) is performed in a tubular reactor that has no moving parts.

20. A mixture comprising: (1) about 50 to 90% by weight, based on the weight of the mixture, of a first oligomer having terminal unsaturation with formula (I): (I) where at least one E1 and E2 is a final group of formula: (II) and wherein only one between E1 and E2 is a final group of formula (II) (*****) where the final group is independently selected from H, TO H. / H or ° \ ^ H and where A, A1 and A2 = independently selected from -H; straight or branched chain alkyl C1-C50, optionally substituted with a group Y; straight or branched chain alkenyl C2-C5o containing 1-5 double bonds, optionally substituted with 1-2 Y groups; cycloalkyl with C5-C8, cycloalkenyl with C-C8; phenyl, (CH2) m-phenyl, 1- or 2-naphthyl; - (CH2) POH, - (CH2CH2?) RoH, - [CH2CH (CH3) OlmH; - (CH2) mSi (ORl) 3, - (CH2) mSi (R1) ÍOR?) 2, - (CHamSi (R?) 2? Ri, - (CH2) mSiíR?) 3; - (Clí2) pr ~ * N O H independently selected from -H, -F, Cl, -Br, Rl; independently selected from -H, -CH Yes- - (CH2) mC02R ?, -F, -Cl, -Br, -I; M1, M2 independently selected from -H, -C = N, - (C = 0) OR1, -F, -Cl, -Br, -I; Straight or branched chain alkyl with Cx-Cs, -OR3, residue from the decomposition of the radical of the azo initiators (azonitrile, azoamidine, cyclic azoamidine, Azolamide, azoalkyl classes); for example -C (R4) 2C = N; Straight chain alkyl or branched straight chain alkenyl or 20 branched C2-Cso containing 1-5 double bonds; cycloalkyl with C5-C8, cycloalkenyl with C5-Cs; phenyl, (CH2) m-phenyl, 1- or 2-naphthyl, -4-benzoylphenyl (wherein any phenyl group can be substituted with up to 2 R2), anthracenyl, anthracenylmethyl; -CCH2) Js (Ri) í > , - (CH2) mNH3wX «; ~ (Clí2) mOW. -ÍCH2CH20) mR *, - (CH2CH (CH3) 0) raRi, -2-í e rahydr of uranyí; -CCH2) mN = C = O; -CH2CnF2n + ?} ~ CH2CH2CnF2a + i, -CH (CF3) 2i -CH2CnF2nH > linear alkanes containing 1-5 epoxy groups derived from vegetable (poly) unsaturated oils; - (CH2) POH, -CHCHABB, H, - [CH2CH (CH3) 0] mH; - (CH2) mSi (ORi) 3) - (CH2) mSi (Ri) (ORi.) 2? - (CH2) mSi (R?) 2? Ri, - (CH2) mSi (Ri) 3; - (CH2) pr-Nw O independently selected from straight or branched chain alkyl Ci-Ca wherein (R1) 2 can constitute a cycloalkyl group with C5-C8; phenyl, -CH2phenyl; straight or branched chain alkyl with Ci-Cβ, straight or branched chain alkoxy C? -C6, -CHO, - (C = 0) 0R1, -N (R1) 2 / ~ N02, - (C = 0) N (R1) 2, -CF3, - (C = 0) OR1, -F, -Cl, -Br, -I; 10 -H, straight or branched chain alkyl C? -C8, -R1 (C = 0), -Rx (C = 0) 0; Ci-Cis straight chain alkyl, Cs-Cg cycloalkyl wherein both 15 adjacent R4 groups can form a 5-8 membered ring, straight or branched chain C? -C8 alkyl groups substituted with C? -C alkoxy; X (-) -F (-), -Cl (-), -Br (-), -I (-), - HS04 (-), -H2P03 (-); -OH, -F, -Cl, -Br, -I, -NH2, -N (R1) 2; m 1-8 25 n 1-18 P 2-8 x 0-49 and 0-49 z 0-49 x + y + z < 49; and (2) about 10% to 50% by weight, based on the weight of the mixture of a second oligomer of Formula (I) where E1 and E2 selected independently of H, A, A1 and A2 = independently selected from -H; straight or branched chain alkyl C? -C50, optionally substituted with a group Y; straight or branched chain alkenyl C2-C5o containing 1-5 double bonds, optionally substituted with 1-2 Y groups; cycloalkyl with C5-C8, cycloalkenyl with C5-C8; phenyl, (CH2) m-phenyl, 1- or 2-naphthyl; - (CH2) pOHJ - (CH2CH20) mH, - [CHaCHCCHs? O H; - (CHa)? ASi (ORi) 3, - (CH2) mSi (Ri.}. (ORi) 2, - (CHa) mSi (Ri) 2? Ri, - (CH2) mSi (Ri) 3; -CCH2) mO (C = 0) CH2. { C = 0) Rí; independently selected from -H, -F, Cl, Br, Rl; G1, G2 independently selected from -H, -CH3; - (CH2) mC02R !, -F, -Cl, -Br, -I; MJ, MZ independently selected from -H, -C = N, - (C = 0) OR1, -F, -Cl, -Br, -I; straight or branched chain alkyl with C? -C8, -OR3, residue of the Decomposition of the radical of the azo initiators (azonitrile, azoamidine, cyclic azoamidine, azoamide, azoalkyl classes); for example -C (R4) 2C = N; Straight or branched chain alkyl with C? -C50, straight or branched chain alkenyl C2-C5o containing 1-5 double bonds; C5-C8 cycloalkyl, cycloalkenyl with Cs-C8; phenyl, (CH2) m-phenyl, 1- or 2-naphthyl, -4-benzoylphenyl (wherein any Phenyl group can be substituted with up to 2 R2), anthracenyl, anthracenylmethyl; - (CH2) mO (C = 0) Ri1- (CH2) m. { C = 0) ORi; linear alkanes containing 1-5 epoxy groups derived from vegetable (poly) unsaturated oils; -CH2) mNíRi) 2} - (CH2) raNH3í +) Xw; - (CH2) ORi, -. { CH2CH2?) FfiRi5 ~ (CH2CHCCH3) 0) mR ?, -2-tetrahy drofuranyl; -CH2CRF2p +? J -CH2CH2C? F2B +? (-CH (CF3) 2! -CHsCJF H, Q / \ - (CH2) m HC CHa - (CH2) POH, -CH2CH2O) I? LH, - [CH2CHCCH3) OlmH; - (CH2) mSi (OR1) 3! - (CH2) mYes (Ri) (ORi.) 2, - (CH2) mSiCRi) 2? Ri > - (CH2) mSi (Ri) 3; - (CH2) mO (C = O) CH2 (C = O) R ?; R independently selected from straight or branched chain alkyl Ci-Cß wherein (R1) 2 can constitute a cycloalkyl group with Cs-C8; phenyl, -CH2phenyl; "straight or branched chain alkyl with straight or branched chain C? -C6 alkoxy C? -C6, -CHO, - (C = 0) 0R1, -N (RX) 2, -N02, - (C = 0) N (R1) 2, -CF3, 10 -. 10 - (C = 0) OR1, -F, -Cl, -Br, -I; -H, straight or branched chain alkyl C? -C8, -R1 (C = 0), -R1 (C = 0) 0; R * straight chain alkyl Cx-Cia, C5-C8 cycloalkyl wherein the two adjacent R4 groups can form a 5-8 membered ring, straight or branched chain C?-C8 alkyl groups substituted with alkoxy 20 C? ~ C; X (-) - F (-), -Cl (-), -Br (-), -I (-), - HS04 (-), -H2P03 (-); -OH, -F, -Cl, -Br, -I, -NH2, -N (R1) 2; 25 m 1-8 1-18 P 2-8 x 0-49 and 0-49 z 0-49 x + y + z < 49.

The mixture of claim 20 wherein the oligomers are formed with at least one unsaturated ethylene glycol monomer selected from the group consisting of n-alkyl methacrylates, branched alkyl methacrylates, cycloalkyl methacrylates, straight or branched chain alkyl methacrylates, alkyl methacrylates aromatics, aromatic methacrylates, hydroxyalkyl methacrylates, heterocyclyl methacrylates, aminoalkyl methacrylates, methacrylates containing ether, methacrylates containing silicone, methacrylamides, methacrylates containing epoxides, unsaturated alkyl methacrylates, methacrylate esters derived from polyunsaturated vegetable oils, terminal alkenes, aralkenes, alkenes of heterocyclyl, dienes, vinyl halides, vinyl esters, vinyl ketones, vinyl functionality containing aldehyde, epoxyalkenes, vinyl monomers, vinylsilanes, alkoxyvinylsilanes, unsaturated diesters and functional methacrylates.

22. A composition, consisting essentially of: (a) at least one oligomer with formula: Z « where A, Ax and A2 = selected 10 independently of -H; straight or branched chain alkyl C1-C50, optionally substituted with a group Y; straight chain alkenyl or 15 branched C2-C50 containing 1-5 double bonds, optionally substituted with 1-2 Y groups; cycloalkyl with C5-C8, cycloalkenyl with C5-C8; Phenyl, (CH 2) m-phenyl, 1- or 2-naphthyl; - (CH2) m0 (C = 0) Ri, - (CH2) m (C = O) OR ?; 25 -NH (C = 0) NH2) -NH (C = 0) NHR ?, -CH2CnFan * ?, -CHaCHaCFito + i. -CH (CF3) 2, -CH2CnF2nH, -CH2 CH2CnF2nH; -P (= 0) (ORi) s; -S (= 0) 2 (ORi); -S (= 0) 2R1; 10 AJ independently selected from -H, -F, Cl, Br, Rl; Ex and E ^ independently selected from -H; fifteen 20 G1, G2 independently selected from -H, -CH3; - (CH2) mC02R ?, -F, -Cl, -Br, -I; and f, and f independently selected from -H, -C = N, - (C = 0) OR1, -F, -Cl, -Br, -I; straight or branched chain alkyl with Ci-Cg, -OR3, residue from the decomposition of the radical of the azo initiators (azonitrile, azoamidine, cyclic azoamidine, azoamide, azoalkyl classes); for example -C (R) 2C = N; 10 R straight or branched chain alkyl with C1-C50, straight or branched chain alkenyl C2-Cso containing 1-5 double bonds; C5-C8 cycloalkyl, cycloalkenyl with Cs-C8; phenyl, (CH2) m-phenyl, 1- or 2-naphthyl, -4-benzoylphenyl (wherein any Phenyl group can be substituted with up to 2 R2), anthracenyl, anthracenylmethyl; - (CHa) mO (C = 0) RV (CH2) m (C = 0) ORi; - (CH2) m (C = 0) Ri -CCH2) m (C = O) NH2j- (CH2) m (C = O) NHRi? 25 -. 25 - (CH2) m (C = O) NH (Ri) 2; - (CH2) mORi, - (CH2CH20) mR?) - (CH2CH (CH3) 0) o1R1, -2-tetral? And drsfuranyl; - (CH2) mN = C = O; -CH2CnF2n + ls -CH2CH2CnF2o + l, -CH (CF3) 2, -CH2CnF2n linear alkanes containing 1-5 epoxy groups derived from vegetable (poly) unsaturated oils; -CCH2) POH, - (CH2CH2O) mHJ - [CH2CHíCH3) O] mH - (CH2) Si (ORi) 3 > - (CH2) mSi. { Ri). { ORi) 2, -íeH2) mSiíR?) 2? Ri, - < CH2) mSiRi - (CH2) ní -N 0 - (CH 2) mO (C = O) CH 2. { C = O) R ?; independently selected from C?-C8 straight or branched chain alkyl wherein (R 1) 2 may constitute a cycloalkyl group with C 5 -C 3; phenyl, -CH2phenyl; straight or branched chain alkyl with Ci-Cs, straight or branched chain alkoxy C? -C6, -CHO, - (C = 0) ORl, -? R ^ z, -N02, - (C = 0) N (R1 ) 2, -CF3, - (C = 0) OR1, -F, -Cl, -Br, -I; -H, straight or branched chain alkyl C? -C8, -R1 (C = 0), -R1 (C = 0) 0; straight chain alkyl C? -C? 8, Cs-C8 cycloalkyl wherein both 10 adjacent R4 groups can form a 5-8 membered ring, straight or branched chain C 1 -C 8 alkyl groups substituted with Ci-C alkoxy; X (-) - F (-), -Cl (-), -Br (-), -I (-), - HS04 (-), -H2P03 (-); -OH, -F, -Cl, -Br, -I, -NH2, -N (R1) 2; m 1-8 20 1-18 2-8 x 0-49 0-49 0-49 25 x + y + z < 49; (b) at least one surfactant; Y (c) water.