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    • 专利摘要:
    ANIONIC HYBRID COPOLYMER COMPOSITION, FORMULATION, INHIBITIVE INCREDITATION COMPOSITION AND INHALATION INHALATION FORMATION IN A WATER SYSTEM Hybrid copolymer compositions include a hybrid copolymer including at least one ethylenically unsaturated hydroxyl transfer agent and at least one hydroxylated unsaturated monomer. as a terminal group; and a hybrid synthetic copolymer including one or more synthetic polymers derived from at least one ethylenically unsaturated monomer with at least one initiator fragment as a terminal group. The hybrid copolymer composition can be prepared as a scale inhibiting composition. Methods of preparing a hybrid copolymer are also included.
    公开号:BR112012001605B1
    申请号:R112012001605-9
    申请日:2010-07-30
    公开日:2021-02-23
    发明作者:Klin A. Rodrigues；Matthew M. Vanderhoof；Allen M. Carrier；Jannifer Sanders
    申请人:Akzo Nobel Chemicals International B.V；
    IPC主号:
    专利说明:

    This application claims the benefit of priority to European Patent Application No. 09175465.5 filed on November 10, 2009 and to U.S. Patent Application No. Serial No. 12 / 689,844, filed on January 19, 2010, which claims Priority benefit to US Patent No. 12 / 533,802, filed on July 31, 2009, and US Patent Application No. Serial No. 11 / 458,180, filed on July 18, 2006, now US Patent No. 7,666,963, which claims priority to US Provisional Patent Application Series No. 60 / 701,380, filed on July 21, 2005. FIELD OF THE INVENTION
    The present invention relates to hybrid copolymers and hybrid copolymer compositions that contain a portion of a naturally occurring oligomer or polymer and a group of a synthetically derived oligomer or polymer. HISTORIC
    Several attempts have been made in the past to use natural materials like polymeric building blocks. These were mainly focused on grafting natural materials such as sugars and starches with synthetic monomers. For example, North American documents numbers 5,854,191, 5,223,171, 5,227,446 and 5,296,470 reveal the use of graft copolymers in cleaning applications.
    The graft with conventional copolymers has been produced by selectively generating initiation sites (for example, free radicals) for the growth of side chains of monomers from the saccharide or polysaccharide backbone (CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, JI Kroschwitz, ed., Wiley-Interscience, New York, 436 (1990)). These grafting techniques typically use Fe (II) salts such as ferrous sulfate or Ce (IV) salts (for example, cerium nitrate or cerium sulfate) to create those initiation sites on the saccharide or polysaccharide skeleton ( see, for example, North American document No. 5,304,620). Such redox processes are not easily controlled and are inefficient. Also, cerium salts tend to be left in the resulting solution as unwanted by-products, thus having a potential negative effect on performance. Therefore, there is a need for natural materials such as polymeric building blocks that do not provide for those problems associated with graft copolymers. SUMMARY OF THE INVENTION
    Compositions of hybrid copolymers and hybrid copolymers derived therefrom contain a portion of a naturally occurring oligomer or polymer and a group of a synthetically derived oligomer or polymer. A conventional method of making hybrid molecules uses water-soluble monomers in the presence of an aqueous solution of a naturally occurring hydroxyl, containing material with a chain transfer agent. Such a method is revealed in the publication of North American document number 20070021577 Al, which is fully incorporated here by reference. However, it has now been discovered that the hybrid copolymers according to the present invention can be prepared with a very high level of naturally derived hydroxyl containing chain transfer agent and additionally retain the functionality of the synthetic polymer portion. In addition, new combinations of naturally derived hydroxyl containing chain transfer agents and ethylenically unsaturated monomers as well as applications for these copolymers that were previously unknown have been discovered.
    In one embodiment, the invention relates to a hybrid copolymer composition comprising a hybrid synthetic polymer and a hybrid copolymer comprising a synthetic polymer derived from at least one ethylenically unsaturated monomer and a naturally derived hydroxyl containing chain transfer agent as a group terminal.
    In another embodiment, the invention is directed to a composition of hybrid anionic copolymers comprising a hybrid synthetic polymer and a hybrid copolymer comprising a synthetic polymer derived from at least one ethylenically unsaturated anionic monomer connected to a naturally derived hydroxyl containing chain transfer agent as a terminal group by a carbonyl group.
    In another embodiment, the invention is directed to a composition of hybrid anionic copolymers comprising a synthetic synthetic polymer and a hybrid copolymer comprising a synthetic polymer derived from at least one ethylenically unsaturated anionic monomer and a naturally derived hydroxyl containing chain transfer agent as a terminal group in which the chain transfer agent is present from an amount greater than about 75% by weight to about 99% by weight, based on the total weight of the hybrid copolymer composition.
    In another embodiment, the invention is directed to a composition of non-anionic hybrid copolymers comprising a hybrid synthetic polymer and a hybrid copolymer comprising a synthetic polymer derived from at least one of an ethylenically unsaturated non-anionic monomer and a naturally derived hydroxyl containing agent chain transfer as a terminal group.
    In a further embodiment, the invention is directed to a method of determining the concentration of a composition of hybrid copolymers in an aqueous system. The method comprises reacting a sample of an aqueous composition of hybrid copolymers comprising a synthetic polymer derived from at least one ethylenically unsaturated anionic monomer and a naturally derived hydroxyl containing chain transfer agent as the end group with an effective amount of photoactivator under efficient conditions to make the hybrid copolymer absorb with a wavelength in the range of 300 to 800 nanometers. The method additionally includes measuring the absorbance of the aqueous sample and comparing the absorbance of the aqueous sample to a predetermined calibration curve of known absorbances and concentrations. The method also includes comparing the absorbance of the aqueous sample to known concentrations and known absorbances to determine the concentration of the hybrid copolymer.
    Additionally "in another embodiment, the invention relates to a method of preparing a hybrid copolymer composition. The method comprises polymerizing at least one monomer with a solution of a naturally derived hydroxyl containing chain transfer agent having a small amount of agents secondary chain transfer.
    In addition to another additional embodiment, the invention is directed to a mixture comprising a composition of hybrid anionic copolymers and a water hardness reducer or a chelating agent. The water hardness reducer or chelating agent is selected from the group consisting of alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal citrates, alkali metal or alkaline earth metal silicate, glutamic acid N, N-diacetic acid (GLDA), methylglycine N, N-diacetic acid (MGDA) and combinations of them. BRIEF DESCRIPTION OF THE DRAWINGS
    The invention is best understood from the following detailed description when dealing with "the accompanying drawings. Included in the drawings are the following figures:
    Figure 1 is a graph detailing the results of dispersion tests conducted for 1 hour comparing a typical polyacrylate / maltodextrin mixture with a hybrid copolymer containing more than 75% by weight of maltodextrin as a chain transfer agent according to one embodiment of the invention.
    Figure 2 is a graph detailing the results of dispersion tests conducted for 24 hours comparing a typical polyacrylate / maltodextrin mixture with a hybrid copolymer containing more than 75% by weight of maltodextrin as a chain transfer agent according to one embodiment of the invention.
    Figure 3 is an illustration of the results after a 1 hour dispersion test between polyacrylate samples having 0% maltodextrin, samples of a hybrid copolymer having at least one ethylenically unsaturated anionic monomer shown with various amounts of maltodextrin present, and a sample having 100% maltodextrin, after a 1 hour dispersion test.
    Figure 4 is a nuclear magnetic resonance ("NMR") spectrum of the graft copolymer of Example 68
    Figure 5 is an Apt NMR spectrum of the graft copolymer of Example 68
    Figure 6 is an NMR spectrum of the hybrid copolymer composition (using azo primer) from Example 69.
    Figure 7 is an Apt NMR spectrum of the hybrid copolymer composition (using azo primer) from Example 69.
    Figure 8 is an NMR spectrum of the graft copolymer composition (using persulfate primer) of Example 70.
    Figure 9 is an Apt NMR spectrum of the graft copolymer composition (using persulfate primer) of Example 70. DETAILED DESCRIPTION OF THE INVENTION
    Generally, the hybrid copolymers of the present invention are formed by preparing compositions of hybrid copolymers in which the transfer of chains from a growing synthetic polymer to a naturally derived hydroxyl containing chain transfer agent occurs. The reaction is expected to proceed according to the following mechanism:
    chain transfer generates a new radical in the naturally derived hydroxyl containing chain transfer agent which then reacts with the synthetic monomer hybrid copolymer composition = mixture of (a) and (b) with a variation in weight% of (a) in composition
    In the first step, initiator I forms free radicals that react with the monomer and initiates the synthetic polymer chain. This then propagates when reacting with 10 different groups of monomers. The termination is then by chain transfer which subtracts a proton from the naturally derived hydroxyl containing chain transfer agent. This terminates the hybrid synthetic polymer (a) and produces a free radical on the naturally derived hydroxyl 15 containing chain transfer agent. The naturally derived hydroxyl containing chain transfer agent then reacts with several groups of monomers to form a species in which the naturally derived hydroxyl containing chain transfer agent is connected to the synthetic polymer chain. This species can then terminate by a chain transfer mechanism or reaction with an initiator fragment or by some other termination reaction such as a combination or disproportionate reaction to produce the hybrid copolymer (b). If the termination is by chain transfer, 10 then Ri is H (taken from naturally derived hydroxyl containing chain transfer agent) and this generates a free radical on another chain transfer agent which can then start another chain.
    Correspondingly, as used herein and as shown in the above reaction, a "hybrid copolymer composition" is a mixture of (a) a hybrid synthetic copolymer and (b) a hybrid copolymer. The composition of hybrid copolymers in this way contains the two groups, (a) and (b), with a minimum amount of the synthetic copolymer 20 hybrid (a) because this component generates the chain transfer that leads to the formation of the hybrid copolymer (b) . One skilled in the art will recognize that the hybrid copolymer composition may contain a certain amount of the unreacted naturally derived hydroxyl containing chain transfer agent. In one embodiment of the invention, the hybrid copolymer composition can be an anionic hybrid copolymer composition. In another embodiment, the hybrid copolymer composition may be a composition of non-anionic copolymers, such as 30 cationic, non-ionic, amphoteric or zwitterionic.
    The term "hybrid copolymer", as defined herein, refers to a copolymer of ethylenically unsaturated monomers with a terminal group containing the naturally derived hydroxyl containing chain transfer agent which is a result of the chain transfer of the hybrid synthetic copolymer. In one embodiment of the invention, the hybrid copolymer has the following structure:
    where C is a naturally derived hydroxyl group containing chain transfer agent, Mhc is the synthetic portion of the hybrid copolymer derived from one or more ethylenically unsaturated monomers and Ri = H from the chain transfer or I from the reaction with the initiator radical or the naturally derived hydroxyl containing chain transfer agent formed by combining two growing chains or another group formed from a termination reaction.
    In one embodiment, the connection point between C and Mhc is through an aldehyde group in C that results in the connection between C and Mhc being a carbonyl group. In another „realization, when the naturally derived hydroxyl containing chain transfer agent is a • 20 saccharide / polysaccharide with an aldehyde group with the reducing terminal group, then the hybrid copolymer can be represented by the structure:

    Where S is a saccharide repeat unit from the saccharide / polysaccharide chain transfer agent es is an integer from 0 to 1000 and p is an integer that is 3, 4 or 5. In another embodiment, when the naturally derived hydroxyl containing chain transfer agent is an oxidized starch that contains aldehyde groups, the hybrid copolymer can be represented by the structure:

    The amount of aldehyde functionality is preferably at least 0.001 mol%, more preferably at least 0.01 mol% the maximum, preferably at least 0.1 mol% of the total anhydrous glucose units in the saccharide / polysaccharide chain transfer agent.
    Also as used herein, the term "hybrid synthetic copolymer" is a synthetic polymer derived from synthetic monomers with a hybrid initiator fragment as a terminal group. The other terminal group is a proton resulting from chain transfer to the naturally derived hydroxyl containing chain transfer agent. As used herein, the term "synthetic monomer" means any ethylenically unsaturated monomer that can undergo free radical polymerization.
    In an embodiment of the invention, an exemplary synthetic synthetic copolymer has the following structure:

    Where I is the initiator fragment, H is the proton taken from the naturally derived hydroxyl containing chain transfer agent and Mhsc is the synthetic portion of the hybrid synthetic copolymer derived from one or more ethylenically unsaturated monomers. One skilled in the art will recognize that if one or more ethylenically unsaturated monomers are used, the average compositions of Mhsc and Mhc will be the same.
    One skilled in the art will recognize that the minimum amount of the hybrid synthetic copolymer will depend on the relative amounts of naturally derived synthetic monomer, initiator and hydroxyl containing chain transfer agent. In addition, in the composition of hybrid copolymers, the amount (amount of chains) of hybrid copolymer (b) will be greater than or equal to the amount of hybrid synthetic copolymer chains (a).
    The molecular weight of the hybrid synthetic polymer is determined by the relative amounts of naturally derived synthetic monomer, initiator and hydroxyl containing chain transfer agent.
    Optionally, in an embodiment of the present invention, the average molecular weight of the hybrid copolymer composition can be less than about 500,000, preferably less than 300,000 and the maximum preferably less than 100,000. In one embodiment of the invention, the average molecular weight of the minimum weight of the natural component is 1000. In an additional embodiment, the composition of hybrid copolymers can be soluble in water. For the purposes of the present application, water soluble is defined as having a solubility greater than about 0.1 gram per 100 grams of water at 25 ° C and preferably 1 gram per 100 grams of water at 25 ° C.
    In another embodiment, the hybrid synthetic copolymer will have a hybrid initiator fragment (I) and some of the hybrid copolymer chains will have a naturally derived hydroxyl containing chain transfer agent at one end and a hybrid initiator fragment (where Ri is I) at the other end of the synthetic polymer chain. As used herein, the term "hybrid primer fragment" is any fragment of the hybrid primer that is incorporated into the hybrid synthetic polymer derived from a hybrid primer. "Hybrid initiators" are free radical initiators or initiation systems excluding initiators or initiation systems based on metal ions. Hybrid initiators are preferably not free radical scavengers but promote chain transfer. In addition, in an embodiment of the invention, the hybrid initiator is soluble in water. Exemplary hybrid initiators include, but are not limited to, peroxides, azo initiators as well as redox systems such as tert-butyl hydroperoxide and erythorbic acid, peroxides such as persulfate and an amine such as hydroxylamine sulfate, sodium formaldehyde sulfoxylate etc. . Hybrid initiators can include both inorganic and organic peroxides. Suitable inorganic peroxides include sodium persulfate, potassium persulfate and ammonium persulfate. Azo initiators, such as water-soluble azo initiators, can also be suitable hybrid initiators. Water-soluble azo initiators include, but are not limited to, 2,2'-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-Azobis [2- (2-imidazolin-2 -yl) propane] disulfate dihydrate, 2,2'-Azobis (2-methylpropionamidine) dihydrochloride, 2,2'-Azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2'-Azobis {2 - [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-Azobis [2- (2-imidazolin-2-yl) propane], 2,2'-Azobis ( 1-imino-1-pyrrolidine-2-ethylpropane) dihydrochloride, 2,2'-Azobis {2-methyl- N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'Azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide] and others. One skilled in the art will recognize that the hybrid initiator fragment incorporated into the hybrid synthetic copolymer will depend on the hybrid initiator used. For example, sodium persulfate, potassium persulfate and ammonium persulfate will incorporate sulfate fragment initiators, while an azo initiator, such as 2,2'-Azobis (2-methylpropionamidine) dihydrochloride, will incorporate a 2-methyl hydrochloride fragment. propane propionamidine. In one embodiment of the invention, the hybrid initiator fragment is not an OH group derived from hydrogen peroxide because hydrogen peroxide in the presence of a metal ion tends to subtract protons from a substrate and creates conventional graft copolymers. In addition, in an embodiment of the invention, the hybrid initiator fragment is soluble in water.
    In one embodiment, I is preferably 0.01 to 20 mol% of Mhc + Mhsc and more preferably I is 0.1 to 15 mol% of Mhc + MhSc and the maximum preferably I is 1 to 10 mol% of Mhc + Mhsc •
    Metal ion initiation systems, such as those containing Fe (II) or Ce (IV) salts, are typically used to create graft copolymers. As noted earlier, conventional graft copolymers are produced by selectively generating initiation sites (eg, free radicals) for the growth of monomer side chains from an existing polymer skeleton (CONCISE ENCYCLOPEDIA OF POLÍMERO SCIENCE AND ENGINEERING, JI Kroschwitz, ed., Wiley-Interscience, New York, 436 (1990)). Therefore, graft copolymers are defined as a skeleton of a natural component such as a polysaccharide with one or more side chains derived from synthetic monomers.
    The mechanism for producing such "graft" copolymers is illustrated below.

    While the graft copolymer may contain a synthetic copolymer component, unlike the hybrid polymer composition, one skilled in the art will recognize that the synthetic polymer is not required in the formation of the graft copolymer. Hence, the greater the amount of synthetic copolymer, the lesser the amount of graft copolymer, as the presence of the synthetic copolymer essentially results in an undesired side reaction in this case and therefore, the synthetic polymer could be considered an impurity in the graft copolymer.
    The term "naturally derived hydroxyl containing chain transfer agent" as used herein, means any hydroxyl containing materials obtained from a renewable source. In an embodiment of the invention, naturally derived hydroxyl containing chain transfer agents include, but are not limited to, small molecules such as glycerol, citric acid, lactic acid, tartaric acid, glyconic acid, ascorbic acid, glycoheptonic acid. The naturally derived hydroxyl containing chain transfer agents may also include saccharides or derivatives thereof. Suitable saccharides include, for example, monosaccharides and disaccharides such as sugars, as well as larger molecules such as oligosaccharides and polysaccharides (for example, maltodextrins, pyrodextrins and starches). In an embodiment of the invention, the naturally derived hydroxyl containing chain transfer agent is maltodextrin, pyrodextrin or a low molecular weight starch or oxidized starch. It has been found that the chain transfer reaction does not work well when the naturally derived hydroxyl containing chain transfer agent is not soluble in the reaction system. For example, high molecular weight starches, such as those having molecular weights in millions or those in granular form, are dispersible in water and not soluble in water. Correspondingly, in embodiments of the invention, the average molecular weight of the chain transfer agent is preferably less than about 500,000 based on a starch standard. Starches having such exemplary molecular weights are soluble in water. In another embodiment, the average molecular weight (Pm) of the chain transfer agent may be less than about 100,000. In addition to another preferred embodiment, the average molecular weight of the chain transfer agent may be less than about 50,000. In addition to another preferred embodiment, the average molecular weight of the chain transfer agent can be less than about 10,000. It has also been determined that for applications where dispersion and fouling control is particularly desirable, a lower molecular weight, such as 10,000, of the chain transfer agent provides improved performance.
    The molecular weight of the polysaccharide was determined by the procedure outlined below:


    The naturally derived hydroxyl containing chain transfer agents can also include cellulose and its derivatives, as well as inulin and its derivatives, such as carboxymethyl inulin. Cellulosic derivatives include 5 plant heteropolysaccharides commonly known as hemicelluloses that are by-products of the pulp and paper industry. Hemicelluloses include xylans, glucuronoxylans, arabinoxylans, glycomanic arabinogalactans, and xyloglycans. Xylans are the most common heteropolysaccharides and are preferred. In addition, these naturally derived hydroxyls containing chain transfer agents also include lignin and its derivatives, such as lignosulfonates. In one embodiment of the invention, cellulosic derivatives such as heteropolysaccharides such as xylans and lignin and their derivatives can be present in an amount of about 0.1% to about 98% by weight, based on the total amount of the hybrid copolymer. In one embodiment of this invention, naturally derived chain transfer agents can be maltodextrins, pyrodextrins and chemically modified versions of maltodextrins and pyrodextrins.
    In another embodiment, the naturally derived chain transfer agent may be inulin cellulose or chemically modified cellulose or inulin or a heteropolysaccharide such as xylan or a lignin derivative, such as lignosulfonate.
    The naturally derived hydroxyl containing chain transfer agents can be used as obtained from its natural source or can be chemically modified. The chemical modification includes hydrolysis by the action of acids, enzymes, oxidants or heat, esterification or etherification. Modified chain transfer agents naturally derived, after undergoing chemical modification, can be cationic, anionic, non-ionic or amphoteric or hydrophobically modified. Such chemical and similar modifications relating to naturally derived hydroxyl containing chain transfer agents are detailed in North American document number US 20070021577 A1, which is incorporated by reference in its entirety here. In one aspect of the present invention, the invention relates to a composition of hybrid anionic copolymers. In an embodiment according to this aspect, the anionic hybrid copolymer composition comprises a hybrid synthetic copolymer and an anionic hybrid copolymer which is a synthetic polymer produced from at least one ethylenically unsaturated anionic monomer that is terminated in a chain, or has a chain a terminal group, with a naturally derived hydroxyl containing chain transfer agent. In a further aspect of the present invention, the anionic hybrid copolymer contains a polymer produced from at least one ethylenically unsaturated anionic monomer attached to the naturally derived hydroxyl containing chain transfer agent through a carbonyl group.
    One skilled in the art will recognize that it is advantageous to have most, if not all, ethylenically polymerized unsaturated monomer. In one embodiment, more than 90% of the ethylenically unsaturated monomer in the hybrid copolymer composition is reacted, in another embodiment, more than 95% of the ethylenically unsaturated monomer in the hybrid copolymer composition is reacted and in one more embodiment, more than 99% of the ethylenically unsaturated monomer in the composition of hybrid copolymers is reacted. In another embodiment, less than 10% of the ethylenically unsaturated monomer in the hybrid copolymer composition is reacted, in another embodiment less than 5% of the ethylenically unsaturated monomer in the hybrid copolymer composition is not reacted and in one more embodiment more than 1% of the monomer ethylenically unsaturated in the composition of hybrid copolymers is not reacted.
    As used herein, the term "ethylenically unsaturated anionic monomer" means an ethylenically unsaturated monomer that is capable of introducing a negative charge to the anionic hybrid copolymer. These ethylenically unsaturated anionic monomers may include, but are not limited to, acrylic acid, methacrylic acid, ethacrylic acid, a-chloro-acrylic acid, a-cyanoacrylic acid, / 3-methyl-acrylic acid (crotonic acid), a- acrylic phenyl, β-acryloxypropionic acid, sorbic acid, α-chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, β-styryl acrylic acid (l-carboxy-4-phenyl butadiene-1,3), acid itaconic, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxyethylene, muconic acid, 2-acryloxypropionic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodium methyl methyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid, vinyl phosphonic acid and maleic acid. Groups such as maleic anhydride or acrylamide that can be derivatized (hydrolyzed) to groups with a negative charge are also suitable. Combinations of ethylenically unsaturated anionic monomers can also be used. In one embodiment of the invention, the ethylenically unsaturated anionic monomer may preferably be acrylic acid, maleic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methyl propane sulfonic acid or mixtures thereof.
    In an embodiment of the invention, the anionic hybrid copolymer compositions may contain from 1 to 99.5% by weight of the naturally derived hydroxyl containing chain transfer agent based on the weight of the hybrid copolymer composition. Based on the conventional understanding of a person skilled in the art, one could expect that the performance of the inventive anionic hybrid copolymer compositions would decrease as the weight percentage of the chain transfer agent in the polymer increases. For example, polysaccharides have little or no performance as dispersants on their own. Surprisingly, however, it has been found that when the polymer chain transfer agent content is greater than 75% by weight, performance is additionally maintained. For example, the dispersion performance of the anionic hybrid copolymer composition is unexpectedly good even when using large amounts, such as 80, 90, 95 or even 99 and 99.5% by weight, of the polysaccharide as a chain transfer agent. .
    Correspondingly, anionic hybrid copolymer compositions comprise a synthetic synthetic copolymer and an anionic hybrid copolymer containing a naturally derived hydroxyl containing a chain transfer agent such as the termination group, or end group. In embodiments of the invention, the chain transfer agent can optionally be present from amounts greater than 75% by weight to about 99.5%, in another embodiment greater than from about 80 to about 99% by weight, in another embodiment greater than from about 90 to about 99.5% and in addition another embodiment greater than from about 95% to about 99.5%, based on the total weight of the anionic hybrid copolymer composition.
    The anionic hybrid copolymer composition can be used as a constituent of a composition for several different applications including, but not limited to, cleaning, laundry, automatic dishwasher (LLA), superabsorbent, fiberglass binding, rheology modifier, 20 oilfield, water treatment, dispersant, cement and concrete compositions. For cleaning applications, the compositions may include, but are not limited to, detergent, fabric cleaner, automatic dishwasher detergent, rinse aid, glass cleaner, fabric care formulation, fabric softener, flocculants, coagulants, emulsion breakers, alkaline and acid cleaners for smooth surfaces, laundry detergents and others. The compositions can also be used to clean surfaces in industrial and institutional applications. In an exemplary embodiment for automatic dishwasher detergent formulations, such formulations include formulations constructed with phosphate, low phosphate and "zero" phosphate, wherein the detergent is substantially phosphate free.
    As used here, low phosphate means less than 1500 ppm of phosphate in the wash, in another embodiment less than about 1000 ppm of phosphate in the wash, and in additionally another embodiment less than 500 ppm of phosphate in the wash.
    Anionic hybrid copolymer compositions can also be used as scale control agents in cleaning, laundry, ALL, oilfield, water treatment, and in any other aqueous system where scale formation is an issue. Controlled scale includes, but is not limited to, scale based on carbonate, sulfate, phosphate or silicate such as calcium sulfate, barium sulfate, ortho and calcium polyphosphate, tripolyphosphate, magnesium carbonate, magnesium silicate and others. It has been found that suitable scale inhibiting hybrid copolymers will provide at least 80% scale inhibition in a carbonate inhibition test performed according to the procedure detailed in Example 8 of U.S. Patent No. 5,547,612. In embodiments of the invention, hybrid copolymers generally provide more than 80% carbonate inhibition at a dosage level of 100 ppm of the hybrid copolymer in an aqueous system. In additional embodiments, the hybrid copolymers provide better than 80% carbonate inhibition at a dosage level of 25 ppm of the polymer in an aqueous system. In addition to additional embodiments, the hybrid copolymers will provide better than 80% carbonate inhibition at a dosage level of 15 ppm of the polymer in an aqueous system.
    In additional embodiments, the anionic hybrid copolymer compositions can also be used as dispersants in applications in cleaning, oilfield and water treatment, painting and coatings, paper coatings and other applications. These anionic hybrid copolymer compositions can be used to disperse particulates including, but not limited to, minerals, clays, salts, metal ores, metal oxides, dirt, soils, talc, pigments, titanium dioxide, mica, silica, silicates, carbon black, iron oxide, kaolin clay, calcium carbonate, synthetic calcium carbonates, precipitated calcium carbonate, ground calcium carbonate, precipitated silica, kaolin clay or combinations thereof.
    As used herein, the term "anionic hybrid copolymer adjunct ingredient" means ingredients that are optionally used in formulations including the composition of hybrid anionic copolymers. These adjunct ingredients of hybrid anionic copolymers include, but are not limited to, water, surfactants, water hardness reducers, phosphates, sodium carbonate, citrates, enzymes, buffers, perfumes, anti-foaming agents, ion exchangers, bases, anti-redeposition materials, optical brighteners, fragrances, dyes, fillers, chelating agents, fabric bleaching agents, bleaching agents, soap foam control agents, solvents, hydrotropes, bleaching agents, bleaching precursors, buffering agents, removal agents soil, soil release agents, fabric softening agent, opacifiers, water treatment chemicals, corrosion inhibitors, orthophosphates, zinc compounds, tolyltriazole, minerals, clays, salts, metal ores, metal oxides, talc, pigments, titanium dioxide, mica, silica, silicates, carbon black, iron oxide, kaolin clay, modified kaolin clays, calcium carbonate, c carbonates synthetic calcium, fiberglass, cement and aluminum oxide. Surfactants can be anionic, nonionic, such as low-foaming, cationic or zwitterionic nonionic surfactants. In one embodiment of the invention, the chelators can be N glutamic acid, N-diacetic acid (GLDA) and methylglycine N, N-diacetic acid (MGDA) and the like.
    Some other uses in the oil field for the anionic hybrid copolymer compositions of this invention include applications in cementing additives, drilling mud, dispersion and spacer fluid. Often, the water found in oilfield applications is seawater or brine from the formation. The water found in the oil field can be very brackish. Hence, polymers may also desirably be soluble in many brines and brackish waters. These brines can be sea water that contains about 3.5% NaCl by weight or more severe brines that contain, for example, up to 3.5% KC1, up to 25% NaCl and up to 20% CaCl2. Therefore, polymers should be soluble in these systems to be effective as, for example, fouling inhibitors. It was further discovered that the greater the solubility of the anionic hybrid copolymer compositions in the brine, the greater the compatibility. The composition of synthetic seawater, moderate and severe calcium pickles found that are typical pickles found in the oil field is listed in Table 1 below.Table 1: Typical pickles found in the oil field.

    As described in Table 1, seawater contains about 35 grams per liter of a mixture of salts. Moderate and severe calcium pickles contain about 70 and 200 grams per liter of a mixture of salts respectively.
    In oil field applications, the scale inhibitor can be injected or squeezed, or it can be added from the top to the water produced. Correspondingly, embodiments of the invention also include mixtures of the anionic hybrid copolymer and a carrier fluid. The carrier fluid can be water, glycol, alcohol or oil. Preferably, the carrier fluid is water or brines or methanol. Methanol is often used to prevent the formation of methane hydrate structures (also known as methane clathrate or methane ice) at the bottom of the well. In another embodiment of this invention, the hybrid anionic polymers can be soluble in methanol. In this way, scale inhibiting polymers can be introduced into the well in the methanol line. This is particularly advantageous as there are a fixed number of lines that run into the well and this combination eliminates the need for another line.
    In an embodiment of the invention, the anionic hybrid polymer compositions can be uniformly mixed or combined with water hardness reducers or chelating agents and then processed into powders or granules. For example, compositions including the anionic hybrid copolymer compositions of the present invention can include alkali metal or alkaline earth metal carbonates, citrates or silicates as exemplary water hardeners suitable for use in detergent formulations. The term alkali metals is defined as Group IA elements, such as lithium, sodium and potassium, while alkaline earth metals are Group IIA elements that include beryllium, magnesium and calcium.
    Powders as used herein are defined as having an average particle size of less than about 300 microns, while granules are particles of an average size greater than about 300 microns. By uniformly mixing or combining the hybrid copolymer with the water hardness reducer or chelating agent, the particles or granules provide less hygroscopic properties and allow easier handling and free flowing powders. Free flowing as used in this application are powders or granules that do not agglomerate or fuse with each other. In one embodiment of this invention, the hybrid polymer is an anionic hybrid copolymer. In another embodiment of this invention, water hardness reducers or chelating agents that can be combined with the hybrid copolymer are sodium or potassium carbonate, sodium or potassium silicate, sodium or potassium citrate or N, N glutamic acid -diacetic acid (GLDA) or and methylglycine N, N-diacetic acid (MGDA).
    In another aspect, the present invention relates to compositions of non-anionic hybrid copolymers containing ethylenically unsaturated non-anionic monomers. As used here, an ethylenically unsaturated non-anionic monomer are those that are not anionic. These ethylenically unsaturated non-anionic monomers may include but are not limited to ethylenically unsaturated cationic monomers, ethylenically unsaturated nonionic monomers, ethylenically unsaturated amphoteric monomers and mixtures of ethylenically unsaturated zwitterionic monomers. A composition of non-anionic hybrid copolymers, as used here, is a mixture of a synthetic synthetic copolymer produced from at least one ethylenically unsaturated cationic monomer or at least one ethylenically unsaturated nonionic monomer and a hybrid copolymer comprising a polymer synthetic produced from at least one ethylenically unsaturated cationic monomer or at least one ethylenically unsaturated nonionic monomer that is chain terminated, or has a terminal group, with a naturally derived hydroxyl containing chain transfer agent. As used here, the term "ethylenically unsaturated cationic monomer 5" means an ethylenically unsaturated monomer that is capable of introducing a positive charge • for the composition of non-anionic hybrid copolymers. In one embodiment of the present invention, the ethylenically unsaturated cationic monomer has at least one amine functionality. Cationic derivatives of these non-anionic hybrid copolymer compositions can be formed by forming amino salts of all or a portion of the amine functionality, by making quaternary all or a portion of the amine functionality to form quaternary ammonium salts, or by oxidizing all or a portion of the amine's functionality to form N-oxide groups.
    As used here, the term "amino salt" means that the nitrogen atom of the amine functionality is covalently linked to one to three organic groups and is associated with an anion.
    As used here, the term "quaternary ammonium salt" means that one nitrogen atom of the amine functionality is covalently linked to four. organic groups and is associated with an anion. These 25 cationic derivatives can be synthesized by functionalizing the monomer before polymerization or by functionalizing the polymer after polymerization. These ethylenically unsaturated cationic monomers include, but are not limited to, N, N dialkylaminoalkyl (meth) acrylate, N-alkylaminoalkyl (meth) acrylate, N, N dialkylaminoalkyl (meth) acrylamide and N-alkylaminoalkyl (meth) acrylamide, where the groups are. alkyl are independently cyclic C1-18 compounds such as 1-vinyl imidazole and the like. An aromatic amine containing monomers such as vinyl pyridine can also be used. In addition, monomers such as vinyl formamide, vinyl acetamide and the like that generate amine groups on hydrolysis can also be used. Preferably the ethylenically unsaturated cationic monomer is N, N-dimethylaminoethyl methacrylate, tert-butylaminoethylmethacrylate and N, N-dimethylaminopropyl methacrylamide.
    Ethylenically unsaturated cationic monomers that can be used are the quaternized derivatives of the above monomers as well as diallyldimethylammonium chloride also known as dimethyldialylammonium chloride, (meth) acrylamidopropyl trimethylammonium chloride, 2- (meth) acryloyloxy ethyl trimethyl ammonium chloride, 2 - ( met) acryloyloxy ethyl trimethyl ammonium methyl sulfate, 2- (meth) acryloyloxyethyltrimethyl ammonium chloride, N, N-Dimethylaminoethyl (meth) acrylate methyl quaternary chloride, methacryloyloxy ethyl betaine as well as other betaines and sulfobetines, 2- (methyl) acrylate hydrochloride ethyl dimethyl ammonium, 3- (meth) acryloyloxy hydroacetate ethyl dimethyl ammonium, 2- (meth) acryloyloxy chloride ethyl dimethyl cetyl ammonium, 2- (meth) acryloyloxy ethyl diphenyl ammonium chloride and others.
    As used herein, the term "ethylenically unsaturated non-ionic monomer" means an ethylenically unsaturated monomer that does not introduce a charge into the composition of non-anionic hybrid copolymers. These ethylenically unsaturated nonionic monomers include, but are not limited to, acrylamide, methacrylamide, N alkyl (meth) acrylamide, N, N dialkyl (meth) acrylamide such as N, N dimethylacrylamide, hydroxyalkyl (meth) acrylates, alkyl (methyl ) acrylates such as methylacrylate and methylmethacrylate, vinyl acetate, vinyl morpholine, vinyl pyrrolidone, vinyl caprolactam, alkyl, alkylaryl or aryl ethoxylated monomers such as methoxy polyethyleneglycol (methyl) acrylate, allyl glycidyl ether, allyl alcohol, glycerol (methyl), glycerol (methyl) silane, silanol and siloxane functionalities and others. The ethylenically unsaturated nonionic monomer is preferably soluble in water. The preferred ethylenically unsaturated nonionic monomers are acrylamide, methacrylamide, N methyl (meth) acrylamide, N, N dimethyl (meth) acrylamide, vinyl pyrrolidone and vinylcaprolactam.
    The composition of cationic or nonionic hybrid copolymers has a naturally derived hydroxyl containing chain transfer agent as the termination group, or terminal group. This chain transfer agent is preferably present from about 0.1% by weight to about 98%, more preferably from about 10 to about 95% and most preferably from about 20 to about about 75% by weight, based on the total weight of the composition of cationic or nonionic hybrid copolymers.
    In exemplary embodiments, non-anionic hybrid copolymer compositions can be used in fabric softener compositions as well as fabric care compositions. Suitable fabric softener formulations contain fabric softener active substances, 25 water, surfactants, electrolyte, phase stabilizing polymers, perfume, non-ionic surfactant, non-aqueous solvent, silicones, fatty acid, dye, preservatives, optical brighteners, anti-agents -smokers, and mixtures of them. These fabric softener active substances include, but are not limited to, diester quaternary ammonium compounds such as ditallowoyloxyethyl dimethyl ammonium chloride, tallowoyloxyethyl dimethyl ammonium dihydrogen chloride, dicanola-oiloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride , quaternary ammonium cations of triethanolamine ester such as di- (tallowoyloxyethyl hydrogenated) methylN-N, N-methylhydroxyethylammonium and di- (oilyloxyethyl) -N, N-methylhydroxyethylammonium chloride as well as others such as tritallow methyl ammonium chloride, methyl bis (tallow amidoethyl) -2-hydroxyethyl ammonium methyl sulfate, methyl bis (tallow amidoethyl hydrogenated) -2-hydroxyethyl ammonium methyl sulfate, methyl bis (oleyl amidoethyl) -2-hydroxyethyl ammonium methyl sulfate, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, chloride of tallowoiloxyethyl dimethyl ammonium dihydrogen, dicanola-oiloxyethyl dimethyl ammonium chloride, N-tallowoiloxyethyl-N-tallowoilaminopropyl m ethyl amine, 1,2-bis chloride (hardened tallowoyloxy) - 3-trimethylammonium propane, dimethyl ammonium tallow chloride and mixtures of these.
    Preferred actives are diester quaternary ammonium compounds (DEQA) which are typically obtained by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials that typically result from such reactions include N, N-di (acyloxyethyl) -N, N-dimethylammonium chloride or N, N-di (acyloxyethyl) -methyl, N, N-methylhydroxyethylammonium in which the acyl group is derived from animal, unsaturated, and polyunsaturated fats, fatty acids, for example, oleic acid, and / or partially hydrogenated fatty acids, derived from vegetable oils and / or partially hydrogenated vegetable oils, such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soy oil, tallow oil, rice bran oil, and the like. Those skilled in the art will recognize that active softener materials made from such processes can comprise a combination of mono-, di-, and tri-esters depending on the process and the starting materials.
    As used herein, the term "tissue care formulation" includes, but is not limited to, formulations used to treat tissue to improve tissue softness, shape retention, tissue elasticity, tissue tensile strength, tissue strength tear tissue, tissue lubrication, tissue relaxation, durable pressing, wrinkle resistance, wrinkle reduction, ease of ironing, abrasion resistance, fabric smoothing, anti-tangle yarn, anti-swelling, freshness, improvement 10 appearance, appearance rejuvenation, color protection, color rejuvenation, anti-shrinkage, static reduction, water absorption or repellency, stain repellency, freshness, anti-microbial, odor resistance, and mixtures thereof. In addition to hybrid non-anionic copolymers, 15 the tissue care formulation may contain ingredients such as cationic surfactants, amphoteric surfactants, fabric softener active substances, sucrose esters, softening agents, other tissue care agents, dispersant groups, such as water, alcohols, 20 diols; emulsifiers, perfumes, wetting agents, viscosity modifiers, pH buffers, antibacterial agents, antioxidants, free radical scavengers, chelators, anti-foaming agents, and mixtures thereof.
    In additional embodiments of the invention, non-anionic hybrid copolymer compositions can be used as flocculants and coagulants for sludge drying and water clarification in wastewater treatment applications. Additionally, domestic and industrial sewage contains material that must be removed. The suspended particles 30 are predominantly stabilized due to their negative net surface charge. The cationic hybrid polymer compositions break this negative charge and allow the removal of suspended solids from water. In addition to additional embodiments, the non-anionic hybrid copolymer compositions function as emulsion breakers for oil-in-water emulsions. These are useful in wastewater treatment applications to meet the limitations of oil fats and greases in the discharge water. In addition, non-anionic hybrid copolymer compositions work with reverse emulsion breakers in the oil field. In this application, small amounts of oil droplets are removed from the continuous water phase before the water can be safely returned to the environment. In addition, hybrid anionic and non-anionic copolymer compositions of the invention can be used in applications requiring film forming characteristics, such as in personal care and / or cosmetic applications.
    Hybrid copolymer compositions can be used in cosmetic and personal care compositions. Compositions of hybrid copolymers useful in cosmetic and personal care compositions include both anionic and non-anionic hybrid copolymer compositions. Cosmetic and personal care compositions include, for example, skin lotions and creams, skin gels, serums and liquids, facial and body cleansers, wipes, liquid and bar soap, color cosmetic formulations, makeup, foundations , sun care products, sunscreens, sunless tanning formulations, shampoos, conditioners, hair coloring formulations, hair straighteners, products with AHA and butylhydroxytoluene ("BHA") and hair fixatives such as sprays, gels, mousses, ointments, and waxes, including hair fixers with a low content of volatile organic compounds ("VOC") and sunscreens. These cosmetic and personal care compositions can come in any form, including, without limitation, emulsions, gels, liquids, sprays, solids, mousses, powders, wipes, or sticks.
    Cosmetic and personal care compositions contain suitable "cosmetic and personal care active substances". Suitable cosmetic and personal care active agents include, for example, active agents or substances in sunscreen, cosmetic products, conditioning agents, anti-acne agents, antimicrobial agents, anti-inflammatory agents, analgesics, anti-erythema agents, agents antirrutins, anti-edema agents, anti-psoriasis agents, anti-fungal agents, skin protectors, vitamins, antioxidants, free radical removers, anti-irritants, antibacterial agents, antiviral agents, anti-aging agents, photoprotective agents, growth enhancers hair growth inhibitors, hair removal agents, anti-dandruff agents, anti-seborrheic agents, exfoliating agents, healing agents, anti-ectoparasitic agents, sebum modulators, immunomodulators, hormones, plant products, humidifiers, astringents, astringent lotions , enhancements, antibiotics, anesthetics, steroids, tissue healing substances ual, tissue regenerating substances, hydroxyalkyl urea, amino acids, peptides, minerals, ceramides, biohyaluronic acids, vitamins, skin lightening agents, self-tanning agents, coenzyme Q10, niacinimide, capcasin, caffeine, and any combination of any of these .
    Suitable sunscreen agents or active agents useful in the present invention include any particulate active sunscreen that absorbs, spreads, or blocks ultraviolet (UV) radiation, such as UV-A and UV-B. Non-limiting examples of suitable particulate sunscreen agents include clays, agars, guars, nanoparticles, native and modified starches, modified cellulosics, zinc oxide, and titanium dioxide and any combination thereof. Modified starches include, for example, DRY-FLO ^ PC lubricant (aluminum starch octenyl succinate), DRY-FLCHAF lubricant (modified corn starch), DRY-FLO® ELITE LL lubricant (aluminum starch octenyl succinate (e) lauryl lysine), lubricant DRY-FLO® ELITE BN (aluminum starch octenyl succinate (e) boron nitride), all commercially marketed by the National Starch and Chemical Company.
    Sun protection agents can include those that form a physical and / or chemical barrier between UV radiation and the surface to which they are applied. Non-limiting examples of suitable sunscreen agents include ethylhexyl methoxycinnamate (octinoxate), ethylhexyl salicylate (octissalate), butylmethoxydibenzoylmethane, methoxybenzoylmethane, avobenzone, benzophenone-3 (oxybenzone), octocrylene, aminobenzylate, aminobenzoic acid, oxide , octissalate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate and any combination of any of these.
    Cosmetic and personal care compositions can optionally include one or more aesthetic products (i.e., a material that communicates desirable tactile, visual, taste and / or olfactory properties for the surface to which the composition is applied) and can be either hydrophilic or hydrophobic. Non-limiting examples of commercial cosmetic products with "their names in the International Nomenclature of Cosmetic Ingredients (" INCI ") that are optionally suitable for use in the present invention include PURITY <S21C starch (Zea maize starch (corn)) and TAPIOCA PURE ( tapioca starch), as well as combinations thereof, which are marketed by the National Starch and Chemical Company.
    Suitable conditioning agents include, but are not limited to, cyclomethicone; petrolatum; dimethicone; dimethiconol; silicones, such as cyclopentassiloxane and diisostearoyl trimethylolpropane siloxy silicate; sodium hyaluronate; isopropyl palmitate; soy oil; linoleic acid; copolymer of saturated PPG-12 / methylene diphenyldiisocyanate; urea; amodimethicone; trideceth-12; centrimony chloride; diphenyl dimethicone; proprylene glycol; glycerin; hydroxyalkyl urea; tocopherol; quaternary amines; and any combination of them.
    Cosmetic and personal care compositions can optionally include one or more adjuvants, such as pH adjusters, emollients, humectants, conditioning agents, humidifiers, chelating agents, propellants, rheology modifiers and emulsifiers such as gel forming agents, dyes, fragrances, odor masking agents, UV stabilizers, preservatives, and any combination of any of these. Examples of pH adjusters include, but are not limited to, aminomethyl propanol, aminomethylpropane diol, triethanolamine, triethylamine, citric acid, sodium hydroxide, acetic acid, potassium hydroxide, lactic acid, and any combination thereof.
    Cosmetic and personal care compositions can also contain preservatives. Suitable preservatives include, but are not limited to, chlorphenenesin, sorbic acid, disodium ethylenedinitrilotetraacetate, phenoxyethanol, methylparaben, ethylparaben, propylparaben, phytic acid, imidazolidinyl urea, sodium dehydroacetate, benzyl alcohol, methylchlorosothiazolinone and any of them. In one embodiment of the invention, the cosmetic and personal care composition generally contains from about 0.001% to about 20% by weight of preservatives, based on 100% by weight of the total composition. In another embodiment, the composition contains from about 0.1% to about 10% by weight of preservatives, based on 100% by weight of the total composition.
    Cosmetic and personal care compositions can optionally contain thickeners or gel-forming agents. Examples of such gel-forming agents include, but are not limited to, synthetic polymers such as the acrylic-based Carbopol® thickeners series marketed by BF Goodrich, Cleveland, Ohio and associative thickeners such as Aculyn ™, marketed by Rohm & Haas , Philadelphia, Pa. Other exemplary gel-forming agents include cellulosic thickeners, such as derivatized hydroxyethyl cellulose and methyl cellulose, starch-based thickeners, such as acetylated starch, and naturally occurring gums such as agar, algins, gum arabic , guar gum and xanthan gum. Thickeners and rheology modifiers may also include without limitation acrylate copolymer / steareth-20 itaconate, acrylate copolymer / ceteth-20 itaconate, modified potato starch, hydroxypropyl phosphate starch, acrylates / aminoacrylates / C10-30 alkyl copolymer PEG-20 itaconate, carbomer, acrylate crosspolymer / C10-30 alkyl acrylate, hydroxypropylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide (e) isoparaffin C13-14 (e) laureth-7, acrylamide copolymer (e) mineral oil (e) iso-mineral and (e) mineral oil (e) and isopara- and mineral oil (e) and (e) mineral oil 14 (e) polysorbate 85, hydroxyethylacrylate / sodium acrylol dimethyltaurate copolymer, and hydroxyethylacrylate / sodium acrylol dimethyltaurate copolymer.
    In an embodiment of the invention, the cosmetic and personal care composition is a cosmetic composition for hair. Optional conventional additives can also be incorporated into the cosmetic hair compositions of this invention to provide certain modifying properties for the composition. Included among these additives are silicones and 5 silicone derivatives; humectants; humidifiers; plasticizers, such as esters and ethers of glycerin, glycol and phthalate; emollients, lubricants and penetrants, such as lanolin compounds; fragrances and perfumes; UV absorbers; dyes, pigments and other dyes; 10 anti-corrosion agents; antioxidants; detoxifying agents, styling products and conditioning agents; anti-static agents; neutralizers; polishers; preservatives; proteins, protein derivatives and amino acids; vitamins; emulsifiers; surfactants; viscosity modifiers, 15 thickeners and rheology modifiers; gel forming agents; opacifiers; stabilizers; agentessequestrantes; chelating agents; pearlescent agents, aesthetics products; fatty acids, fatty alcohols and triglycerides; botanical extracts; film makers; and 20 clarifying agents. These additives are present in small amounts, efficient to perform their function, and will generally comprise from about 0.01 to about 10% by weight each, and from about 0.01 to about 20% by total weight, based on in the weight of the composition.
    The cosmetic composition for hair can optionally be a mousse. For mousses, the solvent can be a lower alcohol (C1-4), particularly methanol, ethanol, propanol, isopropanol, or butanol, although any solvent known in the art can be used.
    Optionally, an embodiment of the invention can also comprise a spray. Propellant sprays include any optional (any) propellant (s). Such propellants include, without limitation, ethers, such as dimethyl ether; one or more lower boiling hydrocarbons such as single or branched C3-C6 hydrocarbons, for example, propane, butane, and isobutane; halogenated hydrocarbons, such as hydrofluorocarbons, for example, 1,1-difluoroethane and 1,1,1,2-tetrafluoroethane, present as a liquefied gas; and compressed gases, for example, nitrogen, air and carbon dioxide.
    In embodiments of the invention, hybrid copolymer compositions comprising both anionic and non-anionic hybrid copolymer compositions are latently detectable, which means that they will not be detectable in the visible light range until the hybrid copolymer composition comes into contact with a photoactivator. As defined here, the "photoactivator" is an appropriate reagent or reagents that, when present in efficient amounts, will react with the composition of hybrid copolymers, thereby converting the composition of hybrid copolymers into a chemical species that strongly absorbs in the region from around 3 00 up to about 800 nanometers when activated with, for example, sulfuric acid and phenol. In one embodiment of this invention, the activated hybrid copolymer composition will absorb in the region from about 400 to about 700 nanometers.
    A latently detectable group of this invention will be formed from a naturally derived hydroxyl containing chain transfer agent especially when it is a saccharide or polysaccharide group. The photoactivator can be the combination of sulfuric acid and phenol (see Dubois et al, Anal. Chem. 28 (1956) p. 350 and Example 1 of U.S. Patent No. 5,654,198, which is incorporated in its entirety by reference here) . Polymers typically labeled with latently detectable groups exhibit a drop in effectiveness when compared to polymers without these groups. This is especially true when the weight percentage of the latently detectable group is greater than 10 or 20% of the polymer. However, 5 it has been found that the hybrid copolymer compositions of the present invention perform well even when containing 50% or more of the latently detectable group. In this way, the advantages of good performance and prompt detectability are provided, which allow to monitor the system and control fouling without overdosing the fouling control polymer.
    In further embodiments of the present invention the ethylenically unsaturated monomer of the ester ester copolymer composition can optionally be derived from at least one ester monomer. Exemplary ester monomers include, but are not limited to, esters derived from dicarboxylic acid as well as hydroxyalkyl esters. Suitable ester monomers derived from dicarboxylic acid include, but are not limited to, 20 monomethylmaleate, dimethylmaleate, monomethylitaconate, dimethylitaconate, monoethylmaleate, diethylmaleate, monoethylitaconate, diethylitaconate, monobutylaleate, dibutyliteate, dibutyliteate and dibutyliteate. Suitable hydroxyalkyl esters include, but are not limited to, 25 a, hydroxy ethyl (meth) acrylate, hydroxy propyl (meth) acrylate, hydroxy butyl (meth) acrylate and the like.
    In a further aspect, the invention relates to a method of preparing a hybrid copolymer composition. The method of preparing the hybrid copolymer composition 30 comprises reacting at least one monomer with a solution of a naturally derived hydroxyl containing chain transfer agent that includes only small amounts of secondary chain transfer agents, such as sodium hypophosphite. In an embodiment of the invention, the secondary chain transfer agent can be less than 20% by weight of the hybrid polymer. In another embodiment, the naturally derived hydroxyl solution containing chain transfer agent can be substantially free of secondary transfer agents. The method may further comprise catalyzing the polymerization step with an initiator which is substantially free of a metal ion initiation system at a temperature sufficient to activate said initiator.
    In a further aspect, the invention relates to a combination of a hybrid copolymer composition or anionic hybrid copolymer composition and a water hardener or a chelating agent. Exemplary chelating agents suitable for use in the present invention include, but are not limited to, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal citrates, alkali metal or alkaline earth metal silicate, glutamic acid N, N-diacetic acid (GLDA), methylglycine N, N-diacetic acid (MGDA) and combinations of them. In an embodiment according to the invention, the combination can be a particulate containing a uniform dispersion of the hybrid copolymer and the water hardness reducer or chelating agent. The particulate may also be a powder or a granule.
    In yet another aspect, when the natural hydroxyl containing chain transfer agent in the composition of hybrid copolymers is a saccharide or a polysaccharide, the invention relates to the number of units of anhydrous glucose that reacted for every 100 units of anhydrous glucose in the copolymer hybrid. As used herein, the term "reacted anhydrous glucose unit" means any anhydrous glucose unit in the composition of hybrid copolymers that does not hydrolyze to glucose. These reacted anhydrous glucose units include those that have synthetic chains attached to them as well as other side reactions that occur in the process such as combining the anhydrous glucose radical with other radicals, adding the synthetic monomer to the anhydrous glucose unit, etc. The number of anhydrous glucose units reacted per 100 anhydrous glucose units in the hybrid is preferably 1 or more, more preferably 2 or more and the maximum preferably 4 or more.
    In yet another aspect, the invention relates to "amphoteric hybrid copolymer compositions" containing both anionic and cationic groups. The anionic groups can be in the naturally derived hydroxyl containing chain transfer agent with the cationic groups in the synthetic component or the cationic groups can be in the naturally derived hydroxyl containing chain transfer agent with the anionic groups in the synthetic component or combinations thereof. When the natural component is a polysaccharide, the anionic material can be an oxidized starch and the cationic group can be derived from ethylenically unsaturated cationic monomers such as diallyldimethylammonium chloride. Alternatively, the oxidized starch itself can first be reacted with a cationic substituent such as 3-chloro-2-hydroxypropyl) trimethylammonium and then reacted with a synthetic anionic or cationic monomer or mixtures thereof. In another embodiment, a cationic starch can be reacted with an anionic monomer. Finally, the cationic and anionic groups can be in the synthetic component of these polymers. These amphoteric hybrid copolymer compositions containing both anionic and cationic groups are particularly useful in detergent formulations such as dispersants and cleaning products. It is understood that these polymers will contain both a natural and a synthetic component. The cationic groups are preferably present in the range of 0.001 to 40 mol% of the anionic groups, more preferably the cationic groups are present in the range of 0.01 to 20 mol% of the anionic groups, and the maximum preferably the cationic groups are present in the 10 range of 0.1 to 10 mol% of anionic groups. Polymers formed from an ethylenically unsaturated cationic monomer tend to have weak toxicological and environmental profiles. Therefore, it is necessary to minimize the level of ethylenically unsaturated cationic monomer in the composition of amphoteric hybrid copolymers. In one embodiment of the invention, when an ethylenically unsaturated cationic monomer is used to produce the amphoteric graft copolymer composition, the ethylenically unsaturated cationic monomer is preferably present in an amount of up to 10 mol% of the ethylenically unsaturated anionic monomer, more preferably the monomer ethylenically unsaturated cationic is preferably present in an amount of up to 6 mol% of the ethylenically unsaturated anionic monomer, and the maximum preferably the ethylenically unsaturated cationic monomer 25 is preferably present in an amount of up to 5 mol% of the ethylenically unsaturated anionic monomer.
    In another aspect, the invention relates to compositions of hybrid anionic copolymers derived from monomers produced from natural sources such as itaconic acid produced from corn or acrylamide produced by fermentation. Acrylamide can be hydrolyzed to acrylic acid after polymerization to introduce anionic functionality. One skilled in the art will recognize that monomers produced from natural sources increase the renewable carbon content of the polymers of this invention. EXAMPLES
    The following examples are intended to exemplify the present invention but are not intended to limit the scope of the invention in any way. The breadth and scope of the invention should be limited only by the claims appended hereto. EXAMPLE 1
    Synthesis of composition of hybrid anionic copolymers with 80% by weight of chain transfer agent.200 grams of maltose as a chain transfer agent (80% aqueous solution of Cargill Sweet Satin Maltose, marketed by Cargill Inc., Cedar Rapids, Iowa) were initially dissolved in 200 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 40 grams of acrylic acid in 120 grams of water 20 was subsequently added to the reactor over a period of 90 minutes. A starter solution comprising 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of 90 minutes. The reaction product was kept at 98 ° C 25 for another 60 minutes. The polymer was then partially neutralized by adding 20 grams of a 50% NaOH solution. The final product was a light yellow solution with 31% solids. EXAMPLE 2
    Synthesis of composition of hybrid anionic copolymers with 95% by weight of polysaccharide functionality. 190 grams of maltodextrin as a polysaccharide chain transfer agent (Cargill MD ™ 01918 dextrin, atomized maltodextrin obtained by enzymatic conversion of common corn starch, marketed by Cargill Inc., Cedar Rapids, Iowa) was initially dissolved 5 in 200 grams of water in a reactor and heated to 95 ° C. A monomer solution containing 10 grams of acrylic acid dissolved in 75 g of water was subsequently added to the reactor over a period of one hour. A starter solution comprising 0.5 grams of sodium persulfate in 25 grams of water was added to the reactor at the same time as the monomer solution but for a period of 1 hour and 10 minutes. The reaction product was maintained at 95 ° C for an additional 30 minutes. The polymer was then partially neutralized by adding 5 grams of a 50% NaOH solution dissolved in 40 grams of water. EXAMPLE 3
    Synthesis of composition of hybrid anionic copolymers with 85% by weight of maltose functionality.213 grams of maltose as a chain transfer agent (80% Cargill Sweet Satin Maltose aqueous solution, marketed by Cargill Inc., Cedar Rapids, Iowa) was initially dissolved in 180 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 30 grams of acrylic acid in 60 grams of water was subsequently added to the reactor over a period of 90 minutes. A starter solution comprising 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of 90 minutes. The reaction product was maintained at 98 ° C 30 for another 60 minutes. The polymer was then partially neutralized by adding 15 grams of a 50% NaOH solution and the final product was a light amber solution. EXAMPLE 4
    Synthesis of composition of hybrid anionic copolymers with 85% by weight of polysaccharide functionality.213 grams of maltodextrin as a polysaccharide chain transfer agent (80% aqueous solution of Cargill Sweet Satin Maltose, marketed by Cargill Inc., Cedar Rapids, Iowa) was initially dissolved in 180 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 30 grams of acrylic acid dissolved in 100 grams of water was subsequently added to the reactor over a period of 90 minutes. A starter solution comprising 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of ninety minutes. The reaction product was kept at 98 ° C for another 60 minutes. The polymer was then neutralized by adding 15 grams of a 50% NaOH solution and the final product was an amber solution. EXAMPLE 5
    Synthesis of composition of hybrid anionic copolymers with 90% by weight of maltose functionality.22 5 grams of maltose as a chain transfer agent (80% aqueous solution of Cargill Sweet Satin Maltose, marketed by Cargill Inc., Cedar Rapids, Iowa) was initially dissolved in 200 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 20 grams of acrylic acid in 115 grams of water was subsequently added to the reactor over a period of 90 minutes. A starter solution comprising 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of 90 minutes. The reaction product was maintained at 98 ° C for an additional 60 minutes. The polymer was then partially neutralized by adding 10 grams of a 50% NaOH solution and the final product was a light yellow solution. EXAMPLE 6
    Synthesis of composition of hybrid copolymers _ 5 anionic with 80% by weight of polysaccharide as a chain transfer agent 160 grams of maltodextrin as a polysaccharide chain transfer agent (STAR-DRI 180 DE 18 atomized maltodextrin marketed by Tate and Lile, 10 Decatur, Illinois) was initially dissolved in 200 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 40 grams of acrylic acid in 120 grams of water was subsequently added to the reactor over a period of 90 minutes. A starter solution comprising 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of 90 minutes. The reaction product was kept at 98 ° C for another 60 minutes. The polymer was then partially neutralized by adding 20 grams of a 50% NaOH solution and the final product was a light yellow solution. EXAMPLE 7
    Synthesis of composition of hybrid anionic copolymers with 90% by weight of polysaccharide as an etching agent. chain transfer. 180 grams of maltodextrin as a polysaccharide chain transfer agent (STAR-DRI 180 DE 18 atomized maltodextrin marketed by Tate and Lile, Decatur, Illinois) was initially dissolved in 200 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 20 grams of acrylic acid in 115 grams of water was subsequently added to the reactor over a period of 90 minutes. A starter solution comprising 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of 90 minutes. The reaction product was maintained at 98 ° C for an additional 60 minutes. The polymer was then partially neutralized by adding 10 grams of a 5% 50% NaOH solution and the final product was a light yellow solution. EXAMPLE 8
    Dispersion evaluation of anionic hybrid copolymer compositions.
    The polymers of Example 6 and 7 were evaluated in a clay suspension / dispersion test. A control without any polymer was also tested. These materials were compared against a sample of sodium polyacrylate (NaPAA) (ALCOSPERSE® 602N, marketed by Akzo Nobel Surface Chemistry, Chattanooga, Tennessee). The samples were prepared by adding 2% clay (50:50 pink clay: combined clay from Spinks) to deionized water. The samples were then stirred on a magnetic stirring plate for 20 minutes, after which 0.1% of active polymer was added and the samples were stirred for another minute. The 20 suspensions were then poured into 100ml graduated beakers and left to stand for one hour. The dispersion performance was then rated on a scale of 1 to 5 with 1 being no dispersion and 5 being very good dispersion. The results are shown in Table 2.


    These data in Table 2 above indicate that the polymers of this invention are excellent dispersants. This is especially noteworthy as these polymers contain 80 and 90% polysaccharide but the polysaccharide itself does not have a dispersing performance. In addition, they are comparable in performance to synthetic polymers (eg sodium polyacrylate) typically used in this type of application. EXAMPLE 9
    Synthesis of composition of hybrid anionic copolymers with 85% by weight of natural polysaccharide functionality.170 grams of maltodextrin as a polysaccharide chain transfer agent (Cargill MD ™ 01918 dextrin, atomized maltodextrin obtained by enzymatic conversion of common corn starch, marketed by Cargill Inc., Cedar Rapids, Iowa) was initially dissolved in 250 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 30 grams of acrylic acid in 60 grams was subsequently added to the reactor over a period of 90 minutes. A starter solution comprising 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of 90 minutes. The reaction product was kept at 98 ° C for another 60 minutes. The polymer was then partially neutralized by adding 30 grams of a 50% NaOH solution and the pH of this solution was 7. EXAMPLE 10 -15
    The procedure of Example 9 above was repeated for Examples 10-15 where different levels of sulfonated monomer in the form of sodium 2-acrylamido-2-methylpropane sulfonate (AMPS) were used, as identified in Table 3. This monomer is available as a 50% aqueous solution that was then mixed with the acrylic acid and this mixture of monomers was placed in the reactor for 90 minutes as described above.
    EXAMPLE 16
    The polymers of Examples 9 to 15 were then tested in 3 different brines called Brine 1, 2 and 3 respectively Table 4.

    X: Precipitate formed, structures similar to crystalline fibers or precipitate similar to coarse powder
    The data indicate that the hybrid anionic copolymer compositions of this invention containing acrylic acid and sulfonate monomer and 85% by weight polysaccharide chain transfer agent are compatible with brine. However, a corresponding synthetic homopolymer is not compatible with brine. EXAMPLE 17
    158 grams of maltodextrin as a polysaccharide chain transfer agent (Cargill MD ™ 01960 DE 11, marketed by Cargill Inc., Cedar Rapids, Iowa) was initially dissolved in 155 grams of water in a reactor and heated to 85 ° C. A monomer solution containing 39 grams of acrylic acid and 27.5 grams of a 50% sodium 2-acrylamido-2-methylpropane sulfonate solution was subsequently added to the reactor over a period of 180 minutes. A solution of initiator comprising 8.3 grams of sodium persulfate in 33 grams of water was added to the reactor over a period of 195 minutes. The reaction product was maintained at 85 ° C for an additional 30 minutes. The polymer was then partially neutralized by adding 14.5 grams of a 50% NaOH solution and 66 grams of water. EXAMPLE 18
    The brine compatibility of the sulfonated anionic hybrid copolymer composition containing 75% by weight of maltodextrin from Example 17 and a commercial sulfonated synthetic polymer (Aquatreat 545, marketed by Alco Chemical which is a 2- acrylic acrylamide-2- acrylic acid copolymer) methylpropane sulfonate) was tested in Brine 3, the composition of which is listed in Table 5. The data shown for these compatibility tests are shown below.


    These data indicate that the anionic hybrid copolymer composition of this invention is extremely compatible with brine while corresponding synthetic polymers are not. EXAMPLE 19
    Method for synthesis of a composition of hybrid copolymers with polysaccharide chain transfer agent as well as a secondary chain transfer agent.
    221 grams of maltodextrin as a polysaccharide chain transfer agent (STAR-DRI 100 DE 10 atomized maltodextrin sold by Tate and Lile, Decatur, Illinois Pm 62743, Mn 21406) and 40 g of sodium hypophosphite dihydrate (approximately 7.7% by weight based on the total weight of the polymer) as a secondary chain transfer agent was dissolved in 350 grams of water in a reactor and heated to 75 ° C. A monomer solution containing 221 grams of acrylic acid was subsequently added to the reactor over a period of three hours. A starter solution comprising 11 grams of sodium persulfate in
    80 grams of water was added to the reactor at the same time as the monomer solution for a period of 3.5 hours. The reaction product was maintained at 75 ° C for an additional 60 minutes. The polymer was then partially neutralized by adding 80 grams, 5 of a 50% NaOH solution and the final product was a light yellow solution. EXAMPLE 20
    Synthesis of a composition of hybrid ester copolymers 45.9 grams of monomethylmaleate (ester monomer) was dissolved in 388 grams of water. 15.3 grams of ammonium hydroxide was added and the mixture was heated to 87 ° C. 85 grams of DE 18 maltodextrin (Cargill MD ™ 01918, atomized maltodextrin obtained by enzymatic conversion of common corn starch, marketed by Cargill Inc., Cedar Rapids, Iowa) was added just before the monomer and initiator feeds were started. A monomer solution containing a mixture of 168 grams of acrylic acid and 41.0 grams of hydroxyethyl methacrylate 20 (ester monomer) was added to the reactor over a period of 5 hours. A first initiator solution comprising 21 grams of erythorbic acid dissolved in 99 grams of water was added over a period of 5.5 hours. A second. initiator solution comprising 21 grams of a 25% 70% tertiary butyl hydroperoxide solution dissolved in 109 grams of water was added over a period of 5.5 hours. The reaction product was kept at 87 ° C for 30 minutes. The final product was a clear, clear amber solution and had 34.1% solids. EXAMPLE 21
    The composition of hybrid ester copolymers of Example 20 was evaluated for inhibition of barium sulfate using the procedure described below: PART 1: PREPARING THE SOLUTION
    1. Prepare brine with synthetic sea water ("SW") from the North Sea. The. Add the following salts identified in Table 6 to a glass volumetric flask and make up to volume with deionized water ("Dl"). Weigh all +/- 0.01 grams. B. Buffer the SW by adding 1 drop of acetic acid and then adjust the pH with a saturated sodium acetate solution to reach a pH of 6.1. Record the added quantity. ç. Filter the brine through a 0.45 μm membrane filter under vacuum to remove any dust particles that may affect the test reproducibility.
    NOTE: Biological growth occurs in this solution due to the sulfate content. Use within 1 week of preparation. 2. Preparation of a standard Forties water-forming brine ("FW"). The. Add the following salts identified in Table 7 to a glass volumetric flask and make up to volume with Dl water. Weigh all +/- 0.01 grams. B. Buffer the SW by adding 1 drop of acetic acid and then adjust the pH with a saturated sodium acetate solution to reach a pH of 6.1. Record the added quantity. ç. Filter the brine through a 0.45 μm membrane filter under vacuum to remove any dust particles that may affect the test reproducibility.
    3. Prepare a 1% active polymer solution (10,000 ppm) for each inhibitor to be tested. The. Weigh indicated grams of polymer in a volumetric flask and make up to volume with filtered, buffered seawater.
    Required polymer grams (g) can be calculated using the formula below. g = (V x C) / S where V is the volume in mL of the volumetric flask C is the required polymer concentration (in% by weight) S is the solids (active) content (in% by weight) of the polymer
    Example: A polymer has a solids content of 35%. To create 100mL of a 1% by weight (10,000 ppm) solution: g = (100 x D / 35 = 2,857 g of polymer in 100mL of seawater 4. Prepare a buffer solution a. Add 8.2g of acetate of anhydrous sodium to 100g of Dl water 5. Prepare a cooling solution As barium sulfate forms readily upon cooling, an efficient dose of scale inhibitor is necessary to prevent further precipitation after the test is finished. KC1 to a 3L volumetric flask Dissolve with DI water b.Add 1 active substance in% by weight ALCOFLOW 615 (~ 67.5grams) g = (3000 xl) / 44.4 = 67.57g of polymer in 3000mL c Make up the volume with DI water. PART 2: TEST CONFIGURATION
    6. Label 40mL glass vials with the name and concentration of the inhibitor to be tested and number from 1 to a maximum of 30 samples. The numbers will indicate the race order for the test. 7. Add 15mL of DI water to each vial numbered 1 to 3. These will be used to make the totals. 8. Add 15mL of SW to each vial numbered 4 to 30. 9. Label a second set of glass vials with "FW". 10. Add 15mL of FW to each vial. 11. Place the bottles of FW and SW in an incubator or oven, but do not heat. PART 3: TEST PERIOD
    12. Turn on the incubator and adjust to warm to 80C. 13. Prepare SW for testing. For each bottle of SW numbered 7 to 30, a. Add 0.3mL of sodium acetate buffer solution. B. Add the appropriate amount of fouling inhibitor solution to provide the desired concentration for 30mL of sample.
    Required microliters of inhibitor solution (μl) can be calculated using the formula below. μi = [(Vi x Ci) / C2] x 1000, where Vi is the volume in ml of the test sample (SW + FW) Ci is the desired polymer concentration (in ppm) C2 is the active polymer concentration in. inhibitor solution Example: The desired test concentration is 50 ppm in a sample size of 30 ml (SW + FW). Using a 10,000 ppm (1%) polymer solution: μl = [(30 x 50) / 10,000] x 1000 = 150 μl 14. For each SW bottle numbered 1 to 6, a. Add 0.3mL of sodium acetate buffer solution. B. Add an equivalent amount of water in place of the average amount of scale inhibitor solution used to prepare samples. ç. Vials 1 to 3 will be used to determine ppm of Ba for the totals. d. Vials 4 to 6 will be used to determine ppm of Ba for whites. 15. Heat the solutions for a minimum of 2 hours. 16. At the end of 2 hours, remove a "FW" bottle and the SW labeled with the incubator / greenhouse number 1. 17. Pour the contents of the "FW" bottle into the treated SW. 18. Return sample 1 to the incubator / oven. 19. Set a timer to start counting 2 hours. (This time period is critical.) 20. When 1 minute has passed, remove one and the SW labeled # 2 from the incubator / greenhouse. 21. Return sample 2 to the incubator / oven. 22. Repeat steps 17-19 with the remaining numbered vials, keeping an interval of 1 minute between the samples, until each "FW" has been added to a numbered vial. 23. Label a set of test tubes with information about the inhibitor or race number. These will be used for the filtration step. 24. Weigh 5g +/- 0.02g of cooling solution in 10 each vial. PART 4: FILTRATION
    25. When the 2 hour period is over, remove vial No. 1 from the incubator / oven.
    26. Filter about 5g (record the weight) in 15 previously prepared flask containing cooling solution, making sure that the labels on the flask match. The. Place an open bottle containing cooling solution on a scale. B. Suck sample into a 5 mL syringe with 20 luer-lok. ç. Adjust the syringe with syringe filter with 0.45 μm membrane. d. Weigh 5 grams of filtrate in a flask. Record added filtrate grams (for 25 ppm correction).
    27. Repeat this process with each sample at 1 minute intervals, so that each sample has been under test conditions for exactly 2 hours. PART 5: DETERMINATION OF ppm
    28. The barium concentration must be determined by induced coupled plasma ("ICP"). All samples must be run on the day of the test. 29. The percentage of inhibition can be calculated by the following calculation:% inhibition = ((S * d) -B) / (TB), where S = ppm of Ba in the sample d = dilution factor (grams of filtrate +5 grams of cooling solution) / grams of filtrate B = ppm of Ba on white T = ppm of Ba in total ADDITIONAL TEST INFORMATION:
    SAMPLE MATRIX:
    Materials needed: calcium chloride dihydrate sodium chloride magnesium chloride hexahydrate potassium chloride barium chloride dihydrate sodium sulfate acetic acid sodium acetate polymers to be evaluated ALCOFLOW 615 Necessary equipments:
    Analytical balance Sample vials
    These data in Table 9 below indicate that the hybrid materials are excellent barium sulfate inhibitors and compare well in performance with a commercial synthetic polymer that is used for this purpose.
    1 ALCOFLOW® 300 synthetic polymer for inhibition of barium sulfate scale sold by AkzoNobel Surface Chemistry, Chattanooga, TN.
    The polymers of examples 19 and 20, as identified in Table 12, were also tested for inhibition of calcium carbonate using the test outlined below.
    Calcium carbonate inhibition test protocol:
    One liter of Hardness Solution and an Alkalinity Solution was prepared in deionized water (Dl) using the ingredients and amounts listed in Tables 10 and 11 below:

    A 100 ml polymer solution was prepared by adding 1% active polymer diluted with DI water.
    A sample solution containing the polymer to be tested was prepared in 100 ml volumetric flasks by adding 1.2 grams of Hardness Solution, desired level of the polymer solution (100 microliters of polymer solution = 10 ppm of polymer in the solution aqueous treatment), and 1.2 grams of Alkalinity Solution and using DI water to complete the total solution to 100 ml. A blank solution was prepared like the sample solution above but without the polymer. A total solution was also prepared as the sample solution above but without the polymer and replacing the alkalinity with DI water. The samples were placed without a lid on an oven shaker (Shaker Incubator model Classic C24 from New Brunswick Scientific Co., Inc., Edison, NJ) at 50C, 250 rpm for 17 hours.
    The samples were removed, left to stand in the environment and then 1 ml of each sample was filtered through syringes with a 0.2 micron filter and diluted to a total of 10 grams with 2.5% nitric acid solution.
    The sample solution, blank solution and total solutions were analyzed for calcium and lithium by ICP- Optical Emission Spectrometer ("OES") (model Optima 2000DV from Perkin Elmer Instruments, Covina, CA, with a low standard of 1 ppm of Li, 10 ppm Ca, and a high standard of 2 ppm Li, 20 ppm Ca). After considering the dilution during the filtration process, the% inhibition of calcium carbonate was determined by:

    Where [Ca] Sample [Ca] White [Ca] Totai is the concentration of calcium in the sample, white and total solution respectively and [Li] Sample [Li] Total is the concentration of lithium in the sample and total solution respectively.
    This was the procedure that was used to measure carbonate inhibition in other examples of this patent application.

    These data indicate that although hybrid anionic copolymer compositions containing an ester monomer have 45 to 50% of a polysaccharide chain transfer agent, these polymers perform similarly to a synthetic polymer. This is noteworthy because the polysaccharide used in these examples has no inhibitory performance, although the performance of the hybrid copolymer compositions does not drop even when used at very low levels (typical end-use levels for carbonate inhibiting polymer). calcium are 10 - 15 ppm). EXAMPLE 22
    The hybrid copolymer composition of Example 20 was tested for detectability using the procedure of Example 1 of U.S. Patent No. 5,654,198 and following the procedure of Dubois et al. (Anal Chem. 1956, 28, 350) as shown in Table 13.

    The data indicates that the hybrid copolymer composition of Example 20 is significantly more detectable than the Monomer A marker of Example 1 U.S. 5,654,198. In addition, monomer A is only incorporated into the scale control polymer at about 10% by weight. In this way, the detectability of the hybrid copolymer compositions of this invention is far superior to that of US Patent No. 5,654,198. EXAMPLE 23
    The hybrid copolymer composition synthesized in Example 20 was tested for compatibility in ethylene glycol.

    These data indicate that the hybrid copolymer compositions of the invention are extremely soluble in ethylene glycol. EXAMPLE 24
    The hybrid copolymer composition of Example 20 was tested for compatibility in methanol at a range of concentrations.

    These data indicate that the hybrid copolymer composition of Example 20 is extremely soluble in methanol. EXAMPLE 25
    A zero phosphate dishwasher formulation was formulated containing a hybrid ester copolymer composition (Formulation A) and an anionic hybrid copolymer containing a sulfonate monomer (Formulation B), as shown in Table 15.
    EXAMPLE 26
    Synthesis of composition of hybrid copolymers of ester 34 grams of dimethylmaleate (ester monomer) is dissolved in 150 grams of water. 5.4 grams of ammonium hydroxide is added and the mixture is heated to 87 ° C. 170 grams of DE 18 maltodextrin (Cargill MD ™ 01918, atomized maltodextrin obtained by enzymatic conversion of common corn starch, marketed by Cargill Inc., Cedar Rapids, Iowa) 5 is added immediately before the monomer and initiator feeds are started . A monomer solution containing a mixture of 132.6 grams of acrylic acid and 3.4 grams of hydroxyethyl methacrylate (ester monomer) was added to the reactor over a period of 5 hours.
    A first initiator solution comprising 21 grams of erythorbic acid dissolved in 99 grams of water was added over a period of 5.5 hours. A second initiator solution comprising 21 grams of a 70% tertiary butyl hydroperoxide solution dissolved in 109 grams of water was added over a period of 5.5 hours. The reaction product was kept at 87 ° C for 60 minutes. The final product was a clear, clear amber solution and had 42.0% solids. EXAMPLE 27
    Synthesis of composition of hybrid copolymers of 20 ester 102 grams of monomethylmaleate (ester monomer) was dissolved in 150 grams of water. 5.4 grams of ammonium hydroxide was added and the mixture was heated to 87 ° C. 170 grams of DE 18 maltodextrin (Cargill MD ™ 01918, 25 atomized maltodextrin obtained by enzymatic conversion of common corn starch, marketed by Cargill Inc., Cedar Rapids, Iowa) was added just before the monomer and initiator feeds were started . A monomer solution containing a mixture of 64.6 grams of 30 acrylic acid and 3.4 grams of hydroxypropyl methacrylate was added to the reactor over a period of 5 hours. A first initiator solution comprising 21 grams of erythorbic acid dissolved in 99 grams of water was added over a period of 5.5 hours. A second initiator solution comprising 21 grams of a 70% tertiary butyl hydroperoxide solution dissolved in 109 grams of water was added over a period of 5.5 hours. The reaction product was kept at 87 ° C for 60 minutes. The final product was a clear, clear amber solution and had 41.5% solids. EXAMPLE 28
    Powder formulation for automatic dishwasher with zero phosphate
    EXAMPLE 29
    Anti-redeposition The anionic hybrid copolymers of this invention have been tested for anti-redeposition properties in a generic powder detergent formulation. The powder detergent formulation was as follows:

    The test was conducted in a full-scale washing machine using 3 cotton samples and 3 polyester / cotton samples. The soil used was composed of 17.5 g of pink clay, 17.5 g of combined clay from Spinks and 6.9 g of oil mixture (75:25 vegetable / mineral). The test was conducted for 3 cycles using 100 g of washing powder per wash load. The polymers were dosed in 1.0% by weight of the detergent. The wash conditions used a temperature of 33.9 ° C (93 ° F), 150 ppm hardness and a 10 minute wash cycle.
    The values of L (luminance) a (color component) b (color component) before the first cycle and after the third cycle were measured as Li, ai, bi and L2, a2, b2, respectively, using a spectrophotometer. ΔE (color difference) values were then calculated using the equation below - ΔE = [(Li - L2) 2 + (ai - a2) 2 + (bi - b2) 2] 0.5
    The data shown in Table 16 indicate that the hybrid anionic polymers of this invention have anti-redeposition / soil suspension properties even at low concentrations in the washing liquid (a lower ΔE indicates better anti-redeposition properties). Table 16 - Effect on anti-redeposition / soil suspension
    EXAMPLE 30
    Synthesis of composition of nonionic hybrid copolymers with polysaccharide chain transfer agent
    50 grams of maltodextrin as a polysaccharide chain transfer agent (STAR-DRI 180 DE 18 atomized maltodextrin marketed by Tate and Lile, Decatur, Illinois) was dissolved in 150 grams of water in a reactor and heated to 75 ° C. A monomer solution containing 50 grams of hydroxyethylacrylate was subsequently added to the reactor over a period of 50 minutes. A solution of initiator comprising 2 grams of V-50 [2,2'-Azobis (2 amidino-propane) azo starch dihydrochloride from Wako Pure Chemical Industries, Ltd., Richmond, Virginia] in 30 grams of water was added to the reactor at same time as the monomer solution for a period of 60 minutes. The reaction product was kept at 75 ° C for another 60 minutes. The final product was a white solution almost as clear as water. EXAMPLE 31
    Synthesis of composition of non-anionic hybrid copolymers
    150 grams of maltodextrin as a polysaccharide chain transfer agent (Cargill MD ™ 01918 dextrin, atomized maltodextrin obtained by enzymatic conversion of common corn starch, marketed by Cargill Inc., Cedar Rapids, Iowa) was initially dissolved in 200 grams of water in a reactor and 70 g of HCl (37%) and added and heated to 98 ° C. A monomer solution containing 109 grams of dimethyl aminoethyl methacrylate dissolved in 160 grams of water was subsequently added to the reactor over a period of 90 minutes. A starter solution comprising 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of 90 minutes. The reaction product was kept at 98 ° C for another 60 minutes. The reaction product was then neutralized by adding 14 grams of a 50% NaOH solution and the final product was an amber solution. EXAMPLE 32
    Synthesis of composition of non-anionic hybrid copolymers
    35 grams of Amioca Starch was dispersed in 88 grams of water in a reactor and heated to 52. The starch was depolymerized by the addition of 1.07 grams of concentrated sulfuric acid (98%). The suspension was maintained at 52 ° C for 1.5 hours. The reaction was then neutralized with 1.84 grams of 50% NaOH solution and the temperature was raised to 90 ° C for 15 minutes. The starch gelatinizes and the viscosity has increased during the process and a gel is formed. Viscosity dropped after gelatinization was completed. The temperature was lowered to 72 to 75 ° C. A solution of 8 0.7 grams of dimethyl diallyl ammonium chloride (62% in water) was added to the reactor over a period of 30 minutes. A starter solution comprising 0.2 grams of sodium persulfate in 20 grams of water was added to the reactor at the same time as the monomer solution for a period of 35 minutes. The reaction product was kept at 98 ° C for an additional 2 hours. The final product was a slightly opaque yellow solution. EXAMPLE 33
    Synthesis of composition of non-anionic hybrid copolymers
    35 grams of Amioca Starch was dispersed in 88 grams of water in a reactor and heated to 52. The starch was depolymerized by the addition of 0.52 grams of concentrated sulfuric acid (98%). This is half the acid used in Example 32 and causes less depolymerization of the starch resulting in a higher molecular weight. In this way the molecular weight of the polysaccharide chain transfer agent can be controlled. The suspension was maintained at 52 ° C for 1.5 hours. The reaction was then neutralized with 0.92 grams of 50% NaOH solution and the temperature was raised to 90 ° C for 15 minutes. The starch gelatinizes and the viscosity increased during the process and a gel was formed. Viscosity dropped after gelatinization was completed. The reaction was diluted with 30 grams of water and the temperature was lowered to 72 to 75 ° C. A solution of 80.7 grams of dimethyl diallyl ammonium chloride (62% in water) was added to the reactor over a period of 30 minutes. A starter solution comprising 0.2 grams of sodium persulfate in 20 grams of water was added to the reactor at the same time as the monomer solution over a period of 35 minutes. The reaction product was kept at 98 ° C for an additional 2 hours. The final product was a clear, light yellow solution. EXAMPLE 34
    Synthesis of composition of non-ionic hybrid copolymers with polysaccharide chain transfer agent (inulin)
    50 grams of a polysaccharide chain transfer agent (DEQUEST® PB11620 20% carboxymethyl inulin solution sold by Thermphos) was dissolved in 150 grams of water in a reactor and heated to 75 ° C. A monomer solution containing 50 grams of N, N dimethyl acrylamide was subsequently added to the reactor over a period of 50 minutes. A solution of initiator comprising 2 grams of V-50 [2,2'-azobis (2-amidinopropane) dihydrochloride] azo initiator from Wako Pure Chemical Industries, Ltd., Richmond, Virginia] in 30 grams of water was added to the reactor at same time as the monomer solution for a period of 60 minutes. The reaction product was kept at 75 ° C for another 60 minutes. The reaction product was diluted with 140 grams of water and the final product was a clear, homogeneous amber solution. EXAMPLE 35
    Synthesis of composition of non-anionic hybrid copolymers with polysaccharide chain transfer agent (cellulosic)
    Carboxymethyl cellulose (AQUALON® CMC 9M3ICT marketed by Hercules, Inc., Wilmington, Delaware) was depolymerized as follows. Thirty grams of AQUALON® CMC was introduced into 270 g of deionized water with stirring. 0.03 g of ferrous ammonium sulfate hexahydrate and 2 g of hydrogen peroxide solution (H2O2) (35% active) was added. The mixture was heated to 60 ° C and maintained at that temperature for 30 minutes. This depolymerized CMC solution was then heated to 90 ° C.
    A monomer solution containing 50 grams of acrylamide (50% solution) is subsequently added to the reactor over a period of 50 minutes. A starter solution comprising 2 grams of V-086 2,2'-Azobis [2-methyl-N- (2-hydroxyethyl) propionamide] azo starter from Wako Pure Chemical Industries, Ltd., Richmond, Virginia] in 30 grams of water is added to the reactor at the same time as the monomer solution for a period of 60 minutes. The reaction product is kept at 90 ° C for another 60 minutes. EXAMPLE 36
    Typical diluted fabric softener formulations using non-anionic hybrid copolymers are listed below. TABLE 17 Traditional Diluted Fabric Softener Formulations

    EXAMPLE 37
    Concentrated fabric softener compositions with non-anionic hybrid copolymer compositions are exemplified in Table 18. TABLE 18 Rinse Conditioners Ready for Use in Triple Concentration
    EXAMPLE 38
    Synthesis of a composition of non-anionic hybrid copolymers containing a quaternary amine monomer and a cationic polysaccharide functionality.
    40 grams of Nsight C-1 as a cationic starch chain transfer agent (marketed by AkzoNobel, Bridgewater New Jersey) was initially dissolved in 100 grams of water in a reactor and heated to 98 ° C. A solution of 38.7 grams of dimethyl diallyl ammonium chloride (62% in water) was subsequently added to the reactor over a period of 45 minutes. A starter solution comprising 3.3 grams of sodium persulfate in 20 grams of water was added to the reactor at the same time as the monomer solution for a period of 45 minutes. The reaction product was maintained at 98 ° C for an additional 60 minutes. The final product was a light amber solution. EXAMPLE 39
    The performance of the non-anionic hybrid copolymer composition of Example 38 as an emulsion breaker is tested using the protocol detailed in Example 1 of US 5248449. The synthetic oil in water emulsion is Emulsion No. 3 of this example which is 75% Castrol GTX 10W-40 Engine Oil and 25% Petroleum Sulphate (Petrosul 60). The concentration of the polymer of Example 37 required to break this emulsion was about 100 to 200 ppm. EXAMPLE 40
    The performance of the non-anionic hybrid copolymer composition of Example 38 was tested as a flocculant. 12.5 grams of residual water with suspended particulates (bituminous tailings from an oil field in Canada) was diluted with 12.5 grams of water. 2 grams of the polymer solution of Example 38 was then added and well blended. The suspended particulates flocculated and a layer of clear water was obtained. EXAMPLE 41
    Compositions of non-anionic hybrid copolymers of Examples 32 and 33 are exemplified in the fabric softener compositions listed in Table 19. Table 19 - Fabric softener composition

    EXAMPLE 42
    Synthesis of composition of non-anionic hybrid copolymers
    35 grams of Hilon VII Starch (a starch with high amylose 70% amylose) was dispersed in 132 grams of water in a reactor and heated to 52 ° C. The starch was depolymerized by the addition of 1.07 grams of concentrated sulfuric acid (98%). The suspension was maintained at 52 ° C for 1.5 hours. The reaction was then neutralized with 1.84 grams of 50% NaOH solution and the temperature was raised to 90 ° C for 15 minutes. The starch gelatinizes and the viscosity increased during the process and a gel was formed. Viscosity dropped after gelatinization was completed. The reaction was diluted with 30 grams of water and the temperature was lowered to 72 to 75 ° C. A solution of 100.1 grams of [3- (methacryloylamino) propyl] - trimethylammonium chloride (50% in water) was added to the reactor over a period of 30 minutes. A starter solution comprising 0.2 grams of sodium persulfate in 20 grams of water was added to the reactor at the same time as the monomer solution for a period of 35 minutes. The reaction product was kept at 98 ° C for an additional 2 hours. The final product was a homogeneous white opaque solution. EXAMPLE 43
    Synthesis of composition of non-anionic hybrid copolymers
    35 grams of Amioca Starch was dispersed in 88 grams of water in a reactor and heated to 52. The starch was depolymerized by the addition of 0.52 grams of concentrated sulfuric acid (98%). This is half the acid used in Example 41 and causes less depolymerization of the starch resulting in a higher molecular weight. In this way the molecular weight of the polysaccharide chain transfer agent can be controlled. The suspension was maintained at 52 ° C for 1.5 hours. The reaction was then neutralized with 0.92 grams of 50% NaOH solution and the temperature was raised to 90 ° C for 15 minutes. The starch gelatinizes and the viscosity increased during the process and a gel was formed. Viscosity dropped after gelatinization was completed. The reaction was diluted with 30 grams of water and the temperature was lowered to 72 at 75 ° C. A solution of 66.71 g of [2- (methacryloxy) ethyl] -trimethylammonium chloride (75% in water) was added to the reactor over a period of 30 minutes. A starter solution comprising 0.2 grams of sodium persulfate in 20 grams of water was added to the reactor at the same time as the monomer solution over a period of 35 minutes. The reaction product was kept at 98 ° C for an additional 2 hours. The final product was a homogeneous white opaque paste. EXAMPLE 44
    Clear conditioner shampoo formula A clear conditioner shampoo formula has been prepared using the following ingredients:

    PROCEDURE
    The ingredients are combined in the order listed above. The formulation is mixed until homogeneous after each addition. EXAMPLE 45
    Aerosol suspension mousse formula with 6% VOC Root
    An exemplary aerosol suspension mousse formula with 6% VOC Root has been prepared using the following 10 ingredients:

    PROCEDURE
    Carbopol is slowly sieved into the mixing vortex until it is completely dispersed. While maintaining good agitation, NATROSOL® HHR is then slowly sieved.
    Once dispersed, both AMAZE ™ and Example 31 Polymer are sieved. When the solution is complete, TEA is added. The ingredients in Part B are then added and mixed until smooth. Fitrate and fill aerosol containers. For Part C, load 10 with propellant. EXAMPLE 46
    Combing cream formula for dry / damaged hair
    An exemplary aerosol suspension mousse formula with 6% VOC Root has been prepared using the following ingredients:

    PROCEDURE
    Dissolve STRUCTURE ZEA in water at room temperature. Add the Polymer of Example 33 and heat to 80 ° C while mixing (Phase B). In a separate vessel, combine Phase 5 A and heat to 80 ° C. Add Phase B to Phase A with stirring.
    Add Phase C while maintaining the temperature (80 ° C). Continue mixing and cool to 45 ° C. Add D and adjust the pH if necessary. EXAMPLE 47
    Conditioner Gel Formula
    An exemplary conditioning gel formula was prepared using the following ingredients:

    PROCEDURE
    Place the AMAZE XT powder in the water in Part A and mix until completely hydrated. Separately, combine the ingredients in Part B and mix until dissolved. Add Part B to Part A with stirring. Add the remaining ingredients and mix until uniform. EXAMPLE 48
    Permanent Conditioner Formula
    An exemplary permanent conditioner formula has been prepared using the following ingredients:

    PREPARATION
    Prepare Phase A by dissolving the Polymer of Example 42 in water using good stirring. Mix until the solution is clear and homogeneous. Add dl-panthenol and let 5 dissolve completely. Prepare Phase B by adding TEA to the water and mix well. Add Neo Heliopan and mix until it is clear. Proceed with cationic emulsion DC 929. Combine parts by adding Phase B to Phase A. Mix well and continue mixing for approximately 15 minutes. Add Solu-silk and mix well. Add Versene 100, Glydant, hydroxyethylurea, ammonium lactate, and fragrance, mixing well after each addition. EXAMPLE 49
    Conditioner Clear as suspended bills
    An exemplary clear conditioner with hanging beads was prepared using the following ingredients:

    PROCEDURE
    Poliquaternium-4 is dissolved in water with a mixture.
    The remaining ingredients of Phase A are added sequentially with continuous mixing. Phase B is combined and then added to Phase A. Continue mixing while slowly adding glycolic acid to Phase AB, taking care to avoid air retention. Finally, add the beads slowly while mixing. EXAMPLE 50
    Capillary spray formula with transparent pump with 55% VOC
    An exemplary capillary spray formula with a transparent pump with 55% VOC was prepared using the following

    PREPARATION
    Dissolve AMP in SD Alcohol 40 and water. While maintaining proper stirring, slowly pour into BALANCE 0/55. Add the remaining ingredients and mix until smooth. EXAMPLE 51
    Sunscreen formulas
    Exemplary sunscreen formulas have been prepared using the following ingredients:

    EXAMPLE 52
    Synthesis of composition of hybrid non-ionic copolymers with polysaccharide chain transfer agent Hydroxyethyl cellulose (QP 300 marketed by Dow) was depolymerized as follows. Thirty grams of QP 300 was introduced into 270 g of deionized water with stirring. 0.05 g of ferrous ammonium sulfate hexahydrate and 1 g of hydrogen peroxide solution (H2O2) (35% active) was added. The mixture was heated to 60 ° C and maintained at that temperature for 30 minutes. This depolymerized CMC solution was then heated to 90 ° C.
    A solution of 38.7 grams of dimethyl diallyl ammonium chloride (62% in water) is subsequently added to the reactor over a period of 50 minutes. A starter solution comprising 2 grams of V-086 2,2'-Azobis [2-methyl-N- (2-hydroxyethyl) propionamide] azo starter from Wako Pure Chemical Industries, Ltd., Richmond, Virginia] in 30 grams of water is added to the reactor at the same time as the monomer solution for a period of 60 minutes. The reaction product is maintained at 90 ° C for an additional 60 minutes. EXAMPLE 53
    Synthesis of composition of hybrid anionic copolymers containing 99% polysaccharide chain transfer agent
    A reactor containing 198.0 grams of maltodextrin as a polysaccharide chain transfer agent (Star Dri 180, DE 18 atomized maltodextrin marketed by Tate & Lile, Decatur, Illinois) dissolved in 200.0 grams of water was heated to 95 ° C . A monomer solution containing 2.0 grams of acrylic acid (0.028 moles) and 70.0 grams of water was added to the reactor over a period of 1 hour. A starter solution containing 0.10 grams of sodium persulfate and 30.0 grams of water was added simultaneously over a period of 1 hour and 10 minutes. The reaction product was maintained at 95 ° C for an additional 1 hour. The polymer was then neutralized by adding 1.0 grams of a 50% sodium hydroxide solution. The final product was a clear, light amber solution. EXAMPLE 54
    Synthesis of composition of hybrid anionic copolymers
    A reactor containing 199.0 grams of maltodextrin as a polysaccharide chain transfer agent (Star Dri 180, DE 18 atomized maltodextrin marketed by Tate & Lile, Decatur, Illinois) dissolved in 200.0 grams of water was heated to 95 ° C . A monomer solution containing 1.0 grams of acrylic acid (0.014 moles) and 60.0 grams of water was added to the reactor over a period of 1 hour. A starter solution containing 0.05 grams of sodium persulfate and 30.0 grams of water was added simultaneously over a period of 1 hour and 10 minutes. The reaction product was maintained at 95 ° C for an additional 1 hour. The polymer was then neutralized by adding 0.5 grams of a 50% sodium hydroxide solution. The final product was a clear, light amber solution. EXAMPLE 55
    A reactor containing 75.0 grams of water and 27.8 grams of a 50% sodium hydroxide solution was heated to 100 ° C. A solution containing 50.0 grams of acrylic acid, 25.0 grams of polysaccharide transfer agent maltodextrin (Star Dri 100, DE 10 atomized maltodextrin marketed by Tate & Lile, Decatur, Illinois) and 60.0 grams of water was added to the reactor for a period of 45 minutes. A starter solution containing 3.3 grams of sodium persulfate and 28.0 grams of water was added simultaneously over a period of 1 hour. The reaction product was kept at 100 ° C for an additional 1 hour. The solution was a clear amber color with no crosshair. This illustrates that the reticle can be eliminated by reducing the reactivity of the monomers. In this case, the activity of the monomer was reduced by the addition of 50% NaOH. EXAMPLE 56
    A reactor containing 75.0 grams of water and 18.6 grams of a 50% sodium hydroxide solution was heated to 100 ° C. A solution containing 3 3.5 grams of acrylic acid, 41.5 grams of polysaccharide transfer agent maltodextrin (Star Dri 100, DE 10 atomized maltodextrin marketed by Tate & Lile, Decatur, Illinois) and 60.0 grams of water was added to the reactor for a period of 45 minutes. A starter solution containing 3.3 grams of sodium persulfate and 28.0 grams of water was added simultaneously over a period of 1 hour. The reaction product was kept at 100 ° C for an additional 1 hour. The solution was a clear amber color with no crosshair. This illustrates that the reticle can be eliminated by reducing the reactivity of the monomers. In this case, the activity of the monomer was reduced by the addition of 50% NaOH. EXAMPLE 57
    A series of dispersion tests to prove that hybrid polymers containing more than 75% by weight of chain transfer agent have unexpected performance benefits. Maltodextrin was used as a chain transfer agent. A series of polymers were synthesized containing 33%, 55%, 80%, 85%, 90%, 95%, and 99% and 99.5% maltodextrin and the process for obtaining these samples is described in Examples 55, 56, 1, 3, 5, 2, 53 and 54 respectively.
    The dispersion test was performed as follows: The samples were prepared by adding 2% clay (50:50 pink clay: black clay from Spinks) to the deionized water. The samples were then stirred on a magnetic stirring plate for 20 minutes, after which 0.1% of active dispersant was added and the samples were stirred for another minute. The suspensions were then poured into 100 ml graduated beakers and left to stand. The amount of clear liquid supernatant at the top of the beakers was measured after 1 hour and after 24 hours. The smaller the amount of the clear liquid supernatant, the better the dispersion performance. _. .
    The data in Figure 1 (1 hour) and Figure 2 (24 hours) indicate that a typical maltodextrin (Star Dri 180, DE 18 atomized maltodextrin marketed by Tate & Lile, Decatur, Illinois) chain transfer agent itself does not have any dispersion performance. Figure 3 also illustrates the results after a 1 hour dispersion test between samples of a hybrid copolymer having at least one ethylenically unsaturated anionic monomer shown with maltodextrin present in amounts of 55%, 80%, 95%, 99% and 99.5 %, compared to samples of a polyacrylate (AR4) having 0% maltodextrin present and a sample having 100% maltodextrin (MD) present. A commercial Aquatreat® AR-4 polyacrylate marketed by AkzoNobel Surface Chemistry performs very well. Therefore, as the weight percentage of the chain transfer agent in the hybrid copolymer composition increases, the polymer dispersion performance should decrease (see the dotted line in Figures 1 and 2). Surprisingly, it has been found that the composition of hybrid anionic copolymers containing more than 75% by weight in maltodextrin as a chain transfer agent has good dispersion performance although a drop in performance is expected based on the performance of the polyacrylate and maltodextrin for you. The performance of these copolymers is similar to those containing 33 and 55% by weight of maltodextrin in North American Publication No. 20070021577 (Al). In addition, more surprisingly, the sample containing 99% by weight of maltodextrin has a very good dispersion performance and the performance of the hybrid copolymer compositions begins to drop at the 99.5% chain transfer level (Figure 2). Clearly the polymers of this invention containing more than 75% by weight in chain transfer agent have an unexpected benefit. EXAMPLE 58 ...
    Synthesis of composition of hybrid anionic copolymers containing Lignosulfonate as a chain transfer agent
    102 grams of monomethylmaleate was dissolved in 30 0 0 0 grams of water. 5.4 grams of ammonium hydroxide was added and the mixture was heated to 87 ° C. 340 grams of a naturally derived hydroxyl containing a lignosulfonate as a chain transfer agent (ARBO S08 50% solution marketed by Tembec Chemical Products Group) was added to the reactor. A monomer solution containing a mixture of 64.6 grams of acrylic acid and 3.4 grams of hydroxypropyl methacrylate was added to the reactor over a period of 5 hours. A first initiator solution comprising 21 grams of erythorbic acid dissolved in 99 grams of water was added over a period of 5.5 hours. A second initiator solution comprising 21 grams of a 70% tertiary butyl hydroperoxide solution dissolved in 109 grams of water was added over a period of 5.5 hours. The reaction product was kept at 87 ° C for 60 minutes. The final product was a dark amber / black solution. EXAMPLE 59
    The polymer of Example 58 was evaluated in the anti-redeposition test detailed in Example 29 except that the bleaching delta index (ΔWI) was measured instead of ΔE where, ΔWI = (Li - L2).
    EXAMPLE 60
    The polymer of Example 58 was tested in a phosphate inhibition test described in Example 1 of US 5,547,612.
    Table 21 above indicates that the composition of hybrid anionic copolymers with lignosulfonate of Example 58 is an excellent calcium phosphate inhibitor. EXAMPLE 61
    Synthesis of composition of hybrid amphoteric copolymers containing both anionic and cationic groups.
    150 grams of water was added to 765 grams of RediBond 5330A (marketed by National Starch and Chemical) (27% aqueous solution), and the solution was heated to 40 ° C. The pH of the solution was adjusted to pH 7.0 with 50% sodium hydroxide solution. 0.13 grams of alpha-amylase was added to the solution, which was boiled for 1 hour. 254.7 grams of this pre-digested RediBond 5330A as a cationic polysaccharide chain transfer agent, 2.32 grams of 50% sodium hydroxide solution, and 20.16 grams of monomethyl maleate was heated in a 87 ° reactor Ç. A monomer solution containing 73.88 grams of acrylic acid and 17.96 grams of water was subsequently added to the reactor over a period of 4.5 hours. A starter solution made up of 13.84 grams of erythorbic acid dissolved in 100 grams of water, and a second starter solution made up of 13.98 grams of hydrogen tert-butyl peroxide were added to the reactor at the same time as the starter solution. monomer for a period of 5 hours. The reaction product was cooled and kept at 65 ° C for another 60 minutes. The final product was a brown solution. EXAMPLE 62
    Determination of the number of anhydrous glucose units that reacted per 100 anhydrous glucose units (AGU's) Hydrolysis of the samples
    Before the determination of glucose, the maltodextrins and the various copolymers were hydrolyzed according to the following procedure with sulfuric acid. About 500 mg of sample was weighed in an acid digestion pump equipped with 30 ml of teflon accessory (Parr Instruments) and diluted with 1 ml of 70% H2SO4 followed by the addition of approximately 3 ml of distilled water (milliQ). The mixture was heated to 90 ° C for about 5 hours. This hydrolysis was performed in duplicate for all samples. Glucose determination
    The amount of glucose in the various samples was determined by HPLC, using glycerol as an internal standard. The conditions of the CLAE were as follows:
    Determination of solid content for maltodextrins
    The solid content was determined by treating a known amount of sample in a Mettler Toledo HG63 halogen dryer for 20 minutes. Each analysis was performed in duplicate. Degree of hydrolysis of maltodextrin
    Glucose is representative of the degree of hydrolysis of the maltodextrin portion of the polymer. A theoretical percentage of glucose for a 100% hydrolysis can be calculated for the various samples, since for each of them the exact weight of maltodextrin is known. This theoretical value is the weight of maltodextrin corrected for the addition of one molecule of water per unit of anhydrous glucose, ie: GLUth = [weight of maltodextrin] x 180/162 The efficiency of hydrolysis by the sulfuric acid procedure was established using the initial maltodextrins Star Dri 100 (DE 10) and Star Dri 180 (DE 18). The results are summarized in Table 22, with "the solid content of the samples. The solid content was used to correct for water absorbed in the polymer. Sulfuric table.

    The recovery is slightly lower for the Star Dri 100 (DE 10) sample, but the efficiency of the method is very reasonable. It is important to consider the fact that the maltodextrin samples also contain a certain amount of water. Hydrolysis of copolymers
    The copolymer of Example 20 was hydrolyzed using the procedure detailed above. The copolymer of Example 20 contained 85 grams of DE 18 maltodextrin in approximately 339 grams of polymer. This weight of maltodextrin is corrected for the water content mentioned in Table 22.Table 23: Determination of glucose in hydrolyzed copolymer samples (% w / w)

    The weight percentage of glucose that is unsubstituted was calculated from the results of hydrolysis with sulfuric acid and GLUth. Assuming 100% efficiency of hydrolysis, as only unsubstituted anhydrous glucose 5 units will be hydrolyzed to glucose, the ratio between the 2 values is the percentage of these unsubstituted units in the copolymers, ie units not containing a synthetic chain or not reacted in some other way. The number of anhydrous glucose units reacted per 10 each 100 anhydrous glucose units in the polymer is then 100 minus the% unsubstituted GLU. EXAMPLE 63
    112.6 grams of maltodextrin as a polysaccharide chain transfer agent (STAR-DRI 42R DE 42, 15 weight average molecular weight (Pm) 906, number average molecular weight (Mn) 312, atomized maltodextrin marketed by Tate and Lile , Decatur, Illinois) and 24.2 grams of maleic anhydride were initially dissolved in 102 grams of water in a reactor and heated to 98 ° C. 24.8 grams of 20% sodium hydroxide solution, and an additional 4.6 grams of water were added to the solution in the reactor. A monomer solution containing 36.2 grams of acrylic acid and 150 grams of water was subsequently added to the reactor over a period of 4 hours. A starter solution composed of 4.8 25 grams of sodium persulfate dissolved in 150 grams of water was added to the reactor at the same time as the monomer solution for a period of 4 hours. The reaction product was kept at 98 ° C for another 60 minutes. The final product was a brown solution. The number of anhydrous glucose units 30 reacted per 100 anhydrous glucose units for the polymer of this Example determined by the procedure of Example 62 was 32.6. EXAMPLE 64
    150 grams of maltodextrin as a polysaccharide chain transfer agent (STAR-DRI 180 DE 18 atomized maltodextrin marketed by Tate and Lile, Decatur, Illinois) was initially dissolved in 380 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 50 grams of acrylic acid was subsequently added to the reactor over a period of 90 minutes. A solution of initiator composed of 3.76 grams of initiator 2,2'-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (V 50 marketed by Wako) in 50 grams of water was added to the reactor at same time as the monomer solution for a period of 90 minutes. The reaction product was kept at 98 ° C for another 60 minutes. The final product was a light yellow solution. The number of anhydrous glucose units reacted per 100 anhydrous glucose units for the polymer of this Example determined by the procedure of Example 70 was 4.3 EXAMPLE 65
    150 grams of maltodextrin as a polysaccharide chain transfer agent (Cargill MD 01918 DE 18, Pm 38215, Mn 13644) was initially dissolved in 260 grams of water and 50 grams of acrylic acid. The solution was supplied to a reactor containing 100 grams of water at 98 ° C for a period of 90 minutes. A starter solution composed of 6.6 grams of sodium persulfate in 40 grams of water was added to the reactor at the same time as the monomer solution for a period of 90 minutes. The reaction product was maintained at 98 ° C for an additional 60 minutes. The final product was a light yellow solution. The number of anhydrous glucose units reacted per 100 anhydrous glucose units for the polymer of this Example determined by the procedure of Example 70 was 4.0. EXAMPLE 66
    38 grams of maltodextrin as a polysaccharide chain transfer agent (STAR-DRI 180 DE 18 atomized maltodextrin, Pm 25653, Mn 13744, marketed by Tate and Lile, Decatur, Illinois) were initially 5 dissolved in 160 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 62.8 grams of acrylic acid and 99.4 grams of 50% AMPS solution was subsequently added to the reactor over a period of 120 minutes. A starter solution composed of 5.0 grams of 10 sodium persulfate in 50 grams of water was added to the reactor at the same time as the monomer solution for a period of 120 minutes. The reaction product was maintained at 98 ° C for an additional 60 minutes. The final product was a light yellow solution. The number of anhydrous glucose units 15 reacted per 100 anhydrous glucose units for the polymer of this Example determined by the procedure of Example 70 was 12.6. EXAMPLE 67
    The calcium carbonate inhibition performance on 20 polymer at 15 ppm was determined for the polymers of Example 20, 63, 65 and 66 in Table 24.

    In this test, an inhibition of calcium carbonate above 80% is considered acceptable. These data indicate that polymers having 4 or more anhydrous glucose units reacted for every 100 anhydrous glucose units perform well. EXAMPLE 68 (Comparative example of a graft copolymer)
    150 grams of maltose (marketed by Aldrich) and 0.035 grams of ferrous ammonium sulfate hexahydrate was dissolved in 380 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 50 grams of acrylic acid was subsequently added to the reactor over a period of 1 hour. A starter solution composed of 33.7 grams of 35% hydrogen peroxide solution dissolved in 50 grams of water was added to the reactor at the same time as the monomer solution for a period of 1 hour. The reaction product was kept at 98 ° C for another 60 minutes. EXAMPLE 69
    Maltose hybrid polymer
    150 grams of maltose (marketed by Aldrich) was dissolved in 380 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 50 grams of acrylic acid was subsequently added to the reactor over a period of 1 hour. A starter solution composed of 3.76 grams of V-50 [2.2 'azobis (2-amidinopropane) dihydrochloride sold by Wako] dissolved in 50 grams of water was added to the reactor at the same time as the monomer solution for one 1 hour period. The reaction product was kept at 98 ° C for another 60 minutes. EXAMPLE 70
    Maltose hybrid polymer
    150 grams of maltose (marketed by Aldrich) was dissolved in 380 grams of water in a reactor and heated to 98 ° C. A monomer solution containing 50 grams of acrylic acid was subsequently added to the reactor over a period of 1 hour. A starter solution composed of 3.4 grams of sodium persulfate dissolved in 50 grams of water was added to the reactor at the same time as the monomer solution for a period of 1 hour. The reaction product was kept at 98 ° C for another 60 minutes. EXAMPLE 71
    We collected NMR spectra for the samples of Example 68, 69 and 70. We used maltose as a model compound for the polysaccharide / saccharide in these samples to simplify the spectra and the analysis. Instrument used: MSU Bruker 900 MHz NMR spectrometer.
    All three samples were dissolved in heavy water ("D2O") and analyzed by regular spectroscopy and carbon 13 NMR spectroscopy ("13C") with APT (proton bound test).
    Summary from NMR analysis: 1) Comparing 13C NMR spectra from all three samples, there were several extra 13C signals present in the region from 79 to 105 ppm. All of these extra signals are methoxy oxy carbons except a small amount of quaternary carbons in the region of 98 to 105 ppm (ie, a quaternary acetal carbon) for the Example 69 and 70 hybrid copolymer compositions. These quaternary acetal carbons were not observed for the graft copolymer of Example 68. This indicates that the reaction mechanism of Fe (II) + H2O2 (graft) is different from the chain transfer mechanism of the azo and persulfate primers. This indicates that some amount of the chain transfer occurred in the C 1 acetyl carbons when using azo and persulfate as initiator. There may be a few more points of attachment due to the formation of methoxy-ether bond as evidenced by the presence of some extra signals observed in the region of 79 to 85 ppm. 2) The fingerprint of the global NMR of the graft copolymer of Example 68 is distinguishable from
    Compositions of hybrid copolymers of Example 69 and 70. This is evidenced by the spectra and the summary of the mole% of the different groups in Table 25 below. The spectra of graft copolymers show the presence of ketone functionality and many extra signals in regions of saccharide (58 to 105 ppm) and acid (173 to 178 ppm) that are not present in the spectra of the Example 69 hybrid copolymer compositions and 70. In addition, the graft copolymer spectra show the presence of a significant amount of formic acid (19.6 mol%) compared to little or none of the spectra of the hybrid copolymer compositions of Example 69 and 70. 3) The sample of graft copolymer of Example 68 also contained traces of other free disaccharides and mono sugars but were not measured and listed in Table 25 due to overlapping NMR signals in this sample. 4) 13C NMR signals of polyacrylate were mainly located between 30 and 50 ppm for methino methylene skeleton while the acid functionality is located around 180 ppm.


    The carbonate inhibition of the samples of the copolymer composition of Example 69 and 70 were compared with the graft copolymer of Example 68.

    These data indicate that the carbonate inhibiting performance of the hybrid copolymer compositions of this invention is better than the comparative graft copolymer (carbonate inhibition of 80% or more as measured by this test is considered acceptable). In addition, the fingerprint of the NMR spectra of the Example 69 hybrid copolymer composition is different from the graft copolymer of Example 68 (see Figures 4-9 and Table 25). The hybrid copolymer composition of Example 69 has 6.7 AGUs reacted per 100 AGUs. This indicates that the hybrid Copolymer (b) exists in this composition. However, one skilled in the art will recognize that the azo primer used in Example 69 will not engraft by subtracting a proton from the maltose. Therefore, the hybrid copolymer (b) in the composition of Example 69 is produced by chain transfer. In addition, the NMR fingerprint of Example 70 is similar to that of Example 69, indicating that the persulfate primer also has a chain transfer mechanism. In addition, the Example 70 hybrid copolymer composition has 6.8 AGUs reacted per 100 AGUs. Therefore, both the hybrid copolymer Compositions of Examples 69 and 70 are different from the graft copolymer and are produced by a chain transfer mechanism illustrated in the first part of this application. EXAMPLE 72
    Capillary spray formula with transparent pump with 55% VOC
    An exemplary formula of hair spray with transparent pump with 55% VOC was prepared using the following ingredients:
    PREPARATION
    Dissolve AMP in SD Alcohol 40 and water. While 10 maintains proper stirring, slowly pour into BALANCE 0/55. Add the remaining ingredients and mix until smooth. EXAMPLE 73
    Sunscreen Formulas Exemplary sunscreen formulas have been prepared using the following ingredients:


    All documents cited in the Detailed Description of the Invention are, in part relevant, incorporated herein by reference; the citation of any document should not be interpreted as an admission that it is prior art with respect to the present invention.
    While particular embodiments of the present invention have been illustrated and described here, the invention is not intended to be limited to the details shown. Before that, various modifications can be made in detail within the variation and scope of the claims' equivalents and without departing from the spirit and scope of the invention.
    权利要求:
    Claims (14)
    [0001]
    1. COMPOSITION OF ANIONIC HYBRID COPOLYMER, characterized by comprising: a hybrid copolymer comprising at least one ethylenically anionic unsaturated monomer and a hydroxyl containing chain transfer agent as a terminal group, and a hybrid synthetic copolymer comprising one or more synthetic polymers derived from at least one ethylenically anionic unsaturated monomer with at least one initiator fragment as a terminal group, said hybrid synthetic copolymer having the structure:
    [0002]
    2. COMPOSITION OF ANIONIC HYBRID COPOLYMER, according to claim 1, characterized in that the transfer agent is selected from the group consisting of cellulose, cellulose derivatives, inulin, and inulin derivatives.
    [0003]
    3. COMPOSITION OF ANIONIC HYBRID COPOLYMER, according to any one of claims 1 or 2, characterized in that the hybrid copolymer is soluble in water.
    [0004]
    4. ANYONIC HYBRID COPOLYMER COMPOSITION according to any one of claims 1 to 3, characterized in that the hybrid copolymer has an average molecular weight of less than 100,000.
    [0005]
    5. ANYONIC HYBRID COPOLYMER COMPOSITION according to any one of claims 1 to 4, characterized in that the chain transfer agent has a molecular weight of less than 100,000.
    [0006]
    6. ANYONIC HYBRID COPOLYMER COMPOSITION, according to any one of claims 1 to 5, characterized in that I is derived from a water-soluble initiator.
    [0007]
    7. ANYONIC HYBRID COPOLYMER COMPOSITION, according to any one of claims 1 to 6, characterized in that I is a fragment of an azo or peroxide initiator, with the proviso that the fragment is not a hydroxyl group.
    [0008]
    8. ANIONIC HYBRID COPOLYMER COMPOSITION according to any one of claims 1 to 7, characterized in that the at least one ethylenically anionic unsaturated monomer additionally comprises at least one ester monomer.
    [0009]
    9. ANYONIC HYBRID COPOLYMER COMPOSITION according to claim 8, characterized in that the at least one ester monomer is derived from a dicarboxylic acid or is selected from the group consisting of monomethylmaleate, dimethylmaleate, monomethylitaconate, dimethylitaconate, monoethylmalea, monoethylmalea , monoethylitaconate, diethylitaconate, monobutylmaleate, dibutylmaleate, monobutylacetate and dibutylitaconate.
    [0010]
    10. FORMULATION, characterized in that it comprises the anionic hybrid copolymer composition as defined in any one of claims 1 to 9, wherein the formulation is selected from the group consisting of a cleaning formulation, a superabsorbent formulation, a binding formulation to fiberglass, a rheology modifying formulation, an oil field formulation, a personal care formulation, a water treatment formulation, a dispersing formulation, a scale inhibiting formulation, a cement formulation and a concrete formulation.
    [0011]
    11. FORMULATION according to claim 10, characterized in that it is a cleaning formulation additionally comprising alkali metal or alkaline earth carbonates, citrates or silicates, non-ionic low-foaming surfactants, N, N-acid glutamic acid diacetic (GLDA) or methylglycine N, N-diacetic acid (MGDA).
    [0012]
    12. INHYDRATING INHIBITOR COMPOSITION, characterized in that it comprises the hybrid anionic copolymer composition as defined in any one of claims 1 to 10, wherein the scale-inhibiting composition has a carbonate inhibition greater than 80% at a dosage level of 100 ppm of the hybrid anionic copolymer composition in an aqueous system.
    [0013]
    13. INHYDRATING INHIBITIVE COMPOSITION, according to claim 12, characterized in that said composition has carbonate inhibition greater than 80% at a dosage level of 25 ppm of the hybrid anionic copolymer in the said aqueous system.
    [0014]
    14. METHOD OF INHIBITING INCREDITATION FORMATION IN A WATERFUL SYSTEM, wherein said method is characterized by comprising the addition to said aqueous system of an effective amount of scale inhibitor of the scale inhibiting composition as defined in any of the claims 12 or 13.
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    公开号 | 公开日
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    AR077673A1|2011-09-14|
    JP5620488B2|2014-11-05|
    CN102549034A|2012-07-04|
    AR077672A1|2011-09-14|
    WO2011025624A1|2011-03-03|
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    法律状态:
    2020-01-07| B25A| Requested transfer of rights approved|Owner name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V. (NL) |
    2020-01-14| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-01-28| B07D| Technical examination (opinion) related to article 229 of industrial property law|Free format text: DE ACORDO COM O ARTIGO 229-C DA LEI NO 10196/2001, QUE MODIFICOU A LEI NO 9279/96, A CONCESSAO DA PATENTE ESTA CONDICIONADA A ANUENCIA PREVIA DA ANVISA. CONSIDERANDO A APROVACAO DOS TERMOS DO PARECER NO 337/PGF/EA/2010, BEM COMO A PORTARIA INTERMINISTERIAL NO 1065 DE 24/05/2012, ENCAMINHA-SE O PRESENTE PEDIDO PARA AS PROVIDENCIAS CABIVEIS. |
    2020-07-28| B07G| Grant request does not fulfill article 229-c lpi (prior consent of anvisa)|
    2020-09-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-12-29| B09A| Decision: intention to grant|
    2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 23/02/2021, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/533,802|2009-07-31|
    US12/533,802|US20110028371A1|2009-07-31|2009-07-31|Hybrid copolymers|
    EP09175465.5|2009-11-10|
    EP09175465|2009-11-10|
    US68984410A| true| 2010-01-19|2010-01-19|
    US12/689,844|2010-01-19|
    PCT/US2010/043919|WO2011014783A1|2009-07-31|2010-07-30|Hybrid copolymer compositions|
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