MXPA99003699A

MXPA99003699A - Functional latexes resistant to hydrolysis

Info

Publication number: MXPA99003699A
Application number: MXPA/A/1999/003699A
Authority: MX
Inventors: Wayne Taylor James
Original assignee: Eastman Chemical Company
Priority date: 1996-10-22
Filing date: 1999-04-21
Publication date: 1999-10-14

Abstract

The present invention is directed to a functional latex polymer composition resistant to hydrolysis which contains a vinyl polymer of copolymerizable monoethylenically unsaturated monomers where at least one monomer contains at least one hydrolyzable functional group. The combined oxygen and nitrogen content of the vinyl polymer is up to about 27 wt.%, based on the monomers in the vinyl polymer.

Description

LATEX FUNCTIONAL RESISTANT TO HYDROLYSIS DESCRIPTION OF THE INVENTION The present invention is directed to a polymer latex composition containing at least one hydrolyzable functional group which is resistant to hydrolysis. Latex polymers containing a hydrolyzable functional moiety, such as a large acetoacetoxy group or an enamine formed by the reaction of acetoacetoxy functionality with ammonia or a volatile amine, find utility in coatings, adhesives, sealants, etc. The properties of such latex polymers improve when the large functionality remains unhydrolyzed until a film such as latex is formed and crosslinking occurs. In this way, it is important that functionality be retained during storage and transportation and be available for crosslinking after film formation at the time of use. However, large functionalities, such as acetoacetoxy or enamine, can be hydrolyzed, particularly at elevated temperatures, during storage or transportation in which case the functionality is not available for cross-linking after film formation. U.S. Patent No. 5,484,849 relates to a method for curing vinyl polymers containing acetoacetoxy functionalities where they are dispersed or dissolve the polymers in aqueous solvents. To resist hydrolysis, the acetoacetoxy functionality is transformed into an enamine group by treating the polymer containing the acetoacetoxy group, after preparation and neutralization, with an additional molar equivalent of ammonia or a primary amine such as ethanolamine, methylamine, or isopropylamine. However, the compositions of U.S. Patent No. 5,484,849 still lack the stability, required in most coating applications, for prolonged storage and during transportation, particularly, at elevated temperatures. Thus, a need remains for a latex composition containing large hydrolyzable functionalities, such as acetoacetoxy or enamine functionality, which can be retained substantially unhydrolyzed, during storage and prolonged transportation, particularly, at elevated temperatures. It is an object of the present invention to provide a functional latex composition, resistant to hydrolysis, containing at least one large hydrolysable functional portion. It is a further object of the present invention to provide a method for synthesizing a hydrolysis-resistant functional latex polymer composition, which contains at least one hydrolyzable functionality, such as a large acetoacetoxy group, an enamine formed by reaction / of the acetoacetoxy group with ammonia or a volatile amine, a carbonate group, an epoxide group or an isocyanate group. A novel functional latex polymer composition according to the invention has been synthesized by adjusting the combined oxygen and nitrogen content of the comonomers used to synthesize the functional latex polymer composition containing the hydrolyzable functional group. The polymer contains at least one hydrolyzable functional group, such as a large acetoacetoxy group, an enamine, a carbonate group, an epoxide group or an isocyanate group. A range of combined nitrogen and oxygen content in which the hydrolysable functionality is resistant to hydrolysis has been discovered. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 represents the hydrolysis percentage of acetoacetoxyethyl methacrylate as a function of the oxygen content at different temperatures. Figure 2 represents the fraction of acetoacetoxy enamine functionality that remains as a function of time and oxygen content at 50 ° C. Figure 3 represents the fraction of the acetoacetoxy enamine functionality that remains as a function of time and oxygen content at 10 ° C. Figure 4 represents the stability to the hydrolysis of polymers transported in water containing acetoacetoxy expressed in years to lose 10% of the acetoacetoxy functionality as a function of the oxygen content. Figure 5 represents the stability to the hydrolysis of polymers carried in water containing acetoacetoxy expressed in years to lose - 50% of the acetoacetoxy functionality as a function of the oxygen content. Figure 6 depicts hydrolysis data in an all-vinyl ester-based latex containing a carbonate functional group. Figure 7 represents hydrolysis data in a latex based on acrylic and vinyl ester containing a carbonate functional group. Figure 8 represents hydrolysis data of an acrylic latex (Example 14, 22.7% oxygen content) containing an epoxide functional group. Figure 9 represents hydrolysis data of a latex-acrylic (Example 15, oxygen content 27.7%) containing an epoxide functional group. Figure 10 depicts Arrhenius proportion graphs of epoxide hydrolysis of Examples 14 and 15. Figure 11 depicts the hydrolysis stability of a polymer transported in water containing epoxide, expressed in months to lose 10% of the functionality epoxide, as a function of oxygen content and temperature.

Accordingly, the present invention provides a novel composition with unexpected hydrolytic stability during prolonged storage time and / or at elevated temperatures. A more complete appreciation of the invention and many of the advantages it entails will be readily obtained as soon as it becomes better understood by reference to the figures and the following detailed description. Accordingly, there is provided a hydrolysis-resistant functional latex polymer composition containing a vinyl polymer which is synthesized from monoethylenically copolymerizable unsaturated monomers, one of which contains at least one large hydrolyzable functionality. The combined oxygen and nitrogen content of the copolymerizable monomers is up to 27% by weight, based on the total weight of the monomers, Preferably, the combined oxygen and nitrogen content is up to? 0% and more preferably up to 10%. a particularly preferred embodiment, the combined oxygen and nitrogen content is in the range of about 5 to 22% .The oxygen and nitrogen content of a polymer is determined by the following equations:% oxygen = (total weight of oxygen in monomers) / total weight of monomers) * 100% Nitrogen = (total weight of nitrogen in monomers / total weight of monomers) * 100. Thus, for example, the oxygen content of Example 3 (below) of the present application is calculated as follows: 1 MAM: methyl methacrylate 2 EST: styrene 3 AB: butyl acrylate 4 MAAE: acetoacetoxyethyl methacrylate 5 Note: monomers that polymerize in water and rest on the surface of polymer particles in oxygen content calculations are not used . Example: 2-sodium acrylamido-2-methylpropansulfonate, also coijocido somo AMPS. Calculation of percent oxygen: Percent oxygen = (weight of oxygen / monomers total) * 100 Percent oxygen = (72.7 / 358) * 100 Percent oxygen = 20.3 The polymer composition of functional latex according to. The present invention can be prepared by polymerizing free radicals of monoethylenically unsaturated monomers in emulsion or suspension. The polymer can be a homopolymer or a copolymer of monomers having hydrolyzable functional portions and other monoethylenically unsaturated monomers. A preferred large functional portion according to the present invention is an acetoacetoxy group. An acetoacetoxy group is incorporated into the polymer as a large functionality by polymerizing a monomer containing at least one acetoacetoxy functional moiety. The term "polymer" is used throughout this description to denote a homopolymer or copolymer. A preferred acetoacetoxy functional monomer is represented by the formula (I): R'-CH = C (R!) C (= O) -X'-X3-X3-C (= 0) -CHrC (-0) -R1 (I) wherein R1 is a hydrogen or halogen; R2 is a hydrogen, halogen, alkylthio group of C _-C3, or alkyl group of Ci-C-s; R3 is an alkyl group of Ci-C .; X1 and X3 are independently O, S d a group of the formula: - .. (R1) -, where R1 is an alkyl group of C6C6; X2 is an alkylene group of C2-C12 or a oalkylene group of C3-C__. The alkyl and alkylene groups described herein and in the specification may be linear or branched. The preferred monomers of the formula (I) are (meth) acetoacetoxyethyl ether, acetoacetoxy (meth) ethyl (meth) acrylate, acetoacetoxy propyl (meth) acrylate and acetoacetoxybutyl (meth) acrylate. The term "(meth) acrylate" is used to denote methacrylate or acrylate. A (meth) acrylate of acetoacetoxyethyl (MAAE) is a particularly preferred monomer of formula f). A large acetoacetoxy group, or other large hydrolysable functional portion in a polymer of the invention, is not strictly limited to polymer end groups. Large groups include those groups attached to the main polymer structure and available for further reaction. The amount of the acetoacetoxy-containing monomer may be in the range of 3 to 30% by weight, based on the total amount of the monomers; the preferred amount is 5 to 20% by weight, while the most preferred amount is 12 to 15% by weight based on the total amount of the monomers. A further, preferred, large hydrolysable functional portion according to the present invention is a carbonate group. They are suitable copolymerizable monoethylenically unsaturated monomers containing a monomer carbonate hydrolyzable according to the present invention, for example, those of the general formula (II): R4CH = CH -? - C (?) - C (R4) 3 (II) wherein R4 is independently hydrogen or a group alkyl of C -.- C _._-. Particular monomers of the formula (II) include: CH2 = CH-0-C (0) -C (CH3) 3, CH2 = CH-0-C (O) - 'CH (C2H5) (C4HS), CH2 = CH -0- (= 0) -CH3, CH-CH-0-C (O) -CH2CH3. The amount of a carbonate-containing monomer may be in the range of 2 to 24% by weight based on the total amount of monomers; the preferred amount is 6 to 12% by weight, based on the total amount of monomers. A preferred large hydrolyzable functional portion according to the present invention is an epoxide moiety. Suitable copolymerizable monoethylenically unsaturated monomers containing a hydrolyzable portion of epoxide according to the present invention include those of the general formula (III): R5-R6-R7-R8 (111) wherein R5 is selected from wherein R10 is hydrogen or an alkyl group of C? -C3; Re is selected from the group -C (= 0) -0- or -0-C (= 0) -, - R7 is selected from the group - (-CH2CH2-0) n-CH2CH2-0-C (= 0) - or an alkyl of C? .- C_, wherein n is an integer from 0 to 100; R8 is -CHR9 = CHR9, wherein R9 are the same or different and are selected from hydrogen or methyl group. In addition, R8 may be directly connected to R5, or R8-R7 may be directly connected to R5, or R8 may be connected to group R5-R5. For example, the monomers of the formula (III) include glycidyl (meth) acrylate, allyl glycidyl ether.

In addition, a macromonomer containing at least one epidoxide group is a suitable monomer according to the present invention. The term "macromdnero" is used to denote oligomeric or polymeric materials containing a monoethylenically unsaturated functionality. The amount in per one hundred of an epoxide-containing monomer may be in the range of 2 to 24% by weight based on the total amount of the monomers; the preferred amount is 6 to 12% by weight, based on the total amount of monomers. Another preferred large hydrolyzable functional portion according to the present invention is an isocyanate group. Suitable copolymerizable monoethylenically unsaturated monomers containing an isocyanate hydrolyzable portion according to the present invention include those of the general formula (IV) R "CH = C (R") - Rl- (CR13) 2-NCO (IV) wherein R11 is a hydrogen or a methyl group; R12 is an alkyl group of C? -C2_, a oalkyl group of C3-C3, an aryl group, a group -C (= 0) -0-, or a group -C (= 0) -O-R14, wherein R14 is an alkyl group of C? -C20. Further, in the present application, "aryl" refers to phenyl, naphthyl, or anthracenyl, in which each hydrogen atom can be replaced with an alkyl group of C? -C? _ (Preferably with an alkyl group of Ci? Cβ and more preferably with methyl). In this way, the phenyl may be substituted 1 to 4 times and the naphthyl may be substituted 1 to 6 times. When R12 is phenyl, the bonding of the additional groups, to say: R11CH = C (R11) and (CR13) 2-NCO may be in the ortho, meta or para positions. In addition, "alkyl" in this context refers to a straight or branched chain alkyl group. In addition, a "cycloalkyl" group may have additional C? -C10 alkyl substituents. In addition, R 13 are independently a hydrogen or an "C 3 -C 3 alkyl group." A preferred copolymerizable monoethylenically unsaturated monomer containing an isocyanate moiety is m-isopropenyl-α, α-dimethylbenzyl isocyanate Suitable copolymerizable monoethylenically unsaturated monomers for the preparation of the functional latex polymer composition according to the present invention include, but are not limited to, a monoethylenically unsaturated monomer which may be represented by the general formula (V): CH = C (R15) COOR "(V ) wherein R15 is hydrogen or a C1-C3 alkyl group, and R? e is an alkyl group of C! -C20, phenyl, benzyl, hydroxy- (C1-C4) -alkyl, alkoxy- (Cj.-C_) alkyl, cyclopentyl, cyclohexyl, furyl, C 1 -C alkyl, tetrahydrofuryl, C 1 -C 4 alkyl tetrahydrofuryl and combinations of these monomers thereof. Combinations of monomers are used where R1S is hydrogen and monomers where R15 is an alkyl group to modify the vitreous transition temperature of the functional latex polymer. Preferred examples of comonomers are, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (met) crilato isobutyl, hexyl (meth) acrylate, isoctyl (meth) acrylate, isodecyl (meth) acrylate, methoxyethyl (metha) acrylate, benzyl (meth) acrylate, ethoxyethyl (meth) acrylate, methacrylate ethyl ether, cyclopentyl (meth) acrylate, and isobornyl (meth) acrylic acid, as well as combinations of those monomers thereof. A combination of these monomers may be used in order to achieve an appropriate Tg or other properties for the functional latex polymer. Acrylic and methacrylic acid esters having a C_-C20 alcohol moiety are commercially available or can be prepared by known esterification processes. The acrylic and methacrylic acid ester may contain additional functional groups, such as, hydroxyl, amine, halogen, ether, carboxylic acid, amide, nitrile, and alkyl group. Preferred esters are: (meth) acrylate carbodiimide, methyl (meth) acrylate, ethyl (meth) acrylate, (raet) butyl acrylate, isobutyl (meth) acrylate, ethylhexyl (meth) acrylate, (meth) acrylate octyl, isobornyl (meth) acrylate, allyl (meth) acrylate, and glycidyl (meth) acrylate. Additional suitable copolymerizable monoethylenically unsaturated monomers include styrene monomer. Styrenic monomer denotes styrene, or a substituted styrene such as styrene substituted with ring C_-C3 alkyl, styrene substituted with C3-C3 alkyl or a combination of a styrene substituted with ring and a-alkyl. Preferred styrenic copolymerizable monomers include styrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, α-methylstyrene and combinations thereof. In addition, vinyl esters of the general formula (VI) can be used as copolymerizable monoethylenically unsaturated monomers. RCH = CH-0-C (?) - C (R). (VI) In the formula (2), R is independently hydrogen or an alkyl group of up to 12 carbon atoms. Particular monomers of the formula (VI) include CH2 = CH-0-C (O) -CH3, CH2 = CH-0-C (0) -C. { CH3) 3, CH2 = CH-0-C (0) -CH (C2H5) (C4H9), and CH2 = CH-0-C (0) -CH2CH3. Vinyl ester monomers also include vinyl alcohol vinyl esters such as the VEOVA series available from the Shell Chemical Company as VEOVA 5, VEOVA 9, VEOVA 10 and VEOVA 11 products. See O.W. Smith, M.J. Collins, P.S. Martin, and D.R.Bassett, Prog. Org. Coatings 22, (1993). It should be emphasized that, not only is the hydrolytic stability of a latex polymer increased, but also the hydrolytic stability of a functional moimer that contains a hydrolysable functionality when the oxygen content of the molar mixture used for decreasing is decreased. form the latex polymer composition functional. This is shown in Figure 1, where the percent hydrolysis of acetoacetoxyethyl methacrylate is plotted against the oxygen content at various temperatures. In general, the vinyl monomers are polymerized by a polymerization technique initiated by free radicals in suspension or emulsion. The polymerization can be initiated by a water-soluble or water-dispersible free radical initiator, optionally in combination with a reducing agent, at an appropriate temperature, usually between 55 and 90 ° C. The polymerization of the monomers can be carried out in batch, semi-batch or continuous mode. A conventional surfactant or a combination of surfactant such as an anionic or nonionic emulsifier may be used in the suspension or emulsion polymerization to prepare a polymer of the invention. Examples of preferred surfactants include, but are not limited to, alkali alkyl sulfate or ammonia, alkylsulfonic acid, or fatty acid, oxyethylated alkylphenol, or any combination of anionic or nonionic surfactant. A more preferred monomer of surfactant is HITENOL HS-20 (which is a polyoxyethylene alkyl phenyl ether ammonium sulate available from DKS International, Inc., Japan). A list of surfactants in the treaty is available: McCutcheon's Emulsifiers & Detergents, North American Edition and International Building, MC Publishing Co., Glen Rock, NJ, 1993. The amount of the surfactant used is usually between 0.1 to 6% by weight, based on the total weight of the monomers. Any free radical initiator such as hydrogen peroxide, butylhydroperdioxide, ammonium or alkali sulfate, dibenzoylperoxide, lauryl peroxide, di-tertiarybutylperoxide, 2,2'-azobisisobuteronitrile, benzoylperoxide, and the like can be used as the polymerization initiator. The amount of the initiator is typically between 0.05 to S.0% by weight, based on the total weight of the total monomers. A free radical initiator can be combined with a reducing agent to form a redox initiation system. Suitable reducing agents are those which increase the polymerization rate and include, for example, sodium disulphide, sodium hydrosulphide, sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid and mixtures thereof. The redox system can be used at similar levels as free radical initiators. In addition, they can be used in combination with initiators and reducing agents, polymerization catalysts. Polymerization catalysts are those compounds which increase the polymerization rate by promoting the decomposition of the free radical initiator in combination with the reducing agent in the reaction conditions. Suitable catalysts include transition metal compounds such as, for example, ferrous sulfate heptahydrate (FeS04.7H20), ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixture thereof. In addition, a low level of a chain transfer agent can also be used to prepare a polymer according to the invention. Suitable chain transfer agents include, but are not limited to, butyl ercaptan, n-octylmercaptan, n-dodecyl mercaptan, mercaptopropionate butyl or methyl, mercaptopripidnic acid, 2-ethylhexyl-3-mercaptopropionate, n-butyl-3-mercaptopropionate, isodecyl mercaptan, octadecyl mercaptan, mercaptoacetic acid, haloalkyl compound, (such as carbon tetrabromide and bromodichloromethane), and the reactive chain transfer agents described in U.S. Patent No. 5,247,040, incorporated herein by reference. In particular, mercaptopropionate, allyl mercaptopropionate, allyl mercaptoacetate, crotyl mercaptopropionate and crotyl mercaptoacetate, and mixtures thereof, represent preferred chain transfer agents. In a preferred embodiment of the present invention, a known copolymerizable monomer can be incorporated to promote wet adhesion in the polymer. Examples of monomers that promote wet adhesion include, but are not are limited to nitrogen-containing monomers such as t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N, N-dimethylaminopropylmethacrylamide, 2-t-butylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate and N- (2-methacrylate). -metacryloyloxy-ethyl) ethylene urea. Water-dispersible and water-soluble polymers can also be employed as surfactants or stabilizers according to the present invention. Examples of such polymeric stabilizers include water dispersible polyesters as described in U.S. Patent Nos. 4,946,932 and 4,939,233; water dispersible polyurethanes as described in U.S. Patent Nos. 4,927,876 and 5,137,961; and alkali-soluble acrylic resins as described in U.S. Patent No. 4,839,413, all of which are incorporated herein by reference. Cellulose and polyvinyl alcohols can also be used. Can surfactants and stabilizers be used during the polymerization? to control, for example, the nucleation of particles and growth, particle size and stability or they may be post-aggravated to increase the stability of the latex or modify other properties of the latex such as sour stress, wettability and the like. In a preferred embodiment at least it can be employed an ethylenically unsaturated copolymerizable surfactant. Copolymerizable surfactants having isopropenylphenyl or allyl groups are preferred. The copolymerizable surfactants can be anionic, such as those containing a sulfate or sulfonate group, or nonionic surfactants. Other copolymerizable surfactants include those containing polyoxyethylene alkyl phenyl ether portions. Additional copolymerizable surfactants include sodium alkylallylsulfosuccinate. A preferred molecular weight of the polymer according to the invention is a weight average molecular weight (Mw) of 1,000 to 1,000,000, as determined by gel permeation chromatography (GPC). A more preferred range for the average molecular weight in peqo is from 5,000 to 250,000. A preferred particle size for the aqueous dispersion according to the invention is 0.01 to 25 μm. Thus, in an emulsion polymerization, according to the invention, the particle size of the latex can be in the range of 0.01 to 3 μm. On the other hand, in a suspension polymerization according to the invention, the size of the latex particle may be in the range of 2 to 25 μm. In a preferred embodiment, the particle size of a dispersion formed by emulsion polymerization may be in the range of about 0.05 to about 1.5 μm. A more preferred range is 0.1 to 1.0 μm.

The polymer particles generally have a spherical conformation. In a preferred embodiment, the spherical polymer particle has a core portion and a cover portion or a gradient structure. The core / shell polymer particles can also be prepared in a multi-lobe form, a peanut cover, an acorn form, a raspberry shape or any other shape. It is further preferred, wherein the particles have a core / shell structure that the core portion comprises about 20 to about 80% by weight of the total weight of the particle, and the shell portion comprises about 80 to about 20% by weight of the total weight of the particle. The glass transition temperature (Tg) of the polymer according to the present invention can be up to about 100 ° C. In a preferred embodiment of the present invention, where it is desirable to form a film at ambient temperatures of the particles, the vitreous transition temperature may preferably be below 60 ° C. Functional polymers in enamine represent a preferred derivative of the polymers according to the invention having large acetoacetoxy groups. In aqueous dispersions, the enamine functionality serves to increase the hydrolytic stability of the acetoacetoxy group. The functional polymers in enamine have been described in Polymer Bulletin 32,419-426 (1994). Additionally, the functional polymers in enamine are described in European Patent Application No. 0492847; U.S. Patent No. 5,296,530; and U.S. Patent No. 5,484,849, all of the a-5's are incorporated herein by reference. For example, Figure 2 shows a preferred embodiment where the hydrolysable functionality is an enamine. The amount of the non-hydrolyzed functionality (enamine) remains substantially unchanged in the oxygen content of up to 21% by weight after 1500 hours at 50 ° C; slightly reduced ~ to 26% by weight of oxygen content after 1500 hours at 50 ° C; while substantially hydrolyzed to 29% by weight of oxygen content after less than 500 hours at 50 ° C. It is unexpectedly found that a latex-based All vinyl ester-containing a hydrolyzable carbonate group gives a non-linear response to hydrolysis ran a function of time while an acrylic vinyl ester-based latex containing a hydrolyzable carbonate group gives a linear response. The results of hydrolysis are shown for the two above types of latexes containing a carbonate group in Figures 6 and 7, respectively. Having generally described this invention, further understanding can be obtained by reference to certain specific examples which are provided in present for the purpose of illustration only and not They propose to limit unless otherwise specified. Example 1 Preparation of particles transported in water containing small unstructured acetoacetoxy (latex particles contain 10.9% acetoacetoxyethyl methacrylate (MAAE), oxygen content 10.4). To a 1,000 ml resirca reactor equipped with a condenser, nitrogen purge, and subsurface feed pipe 340 g of water, 15.52 g of HjfTENOL HS-20 (which is a polyoxyethylene alkyl phenyl ether ammonium sulfate available from DKS International) are added. , Inc., Japan), 2.55 g of surfactant TERGITOL NP-40 (70% by weight in water) which is the reaction product of a nonylphenol and about 40 moles of ethylene oxide available from Union Carbide), 3.5 g of sodium carbonate, 9.67 g of styrene, 6.09 g of 2-ethylhexyl acrylate, and 2.15 g of acetoacetoxyethyl methacrylate. A nitrogen purge is started, then the reactor contents are brought to 80 ° C at 400 rpm. After reaching 80 ° C, a solution of the initiator composed of 2.3 g of sodium persulfate dissolved in 13.0 g of water in the reactor is fed into an emulsion feed composed of 120 g of water, and 6.55 g of surfactant AEROSOL is fed. 18 (N-octadecyl sulfosuccinamate anionic surfactant, available from Cytec Industries, Ine), 10.22 g of TERGITOL NP-40 (70% by weight), 183.6 g of styrene (EST), 115.63 g of acrylate of 2-ethylhexyl (2AEH), and 40.81 g of acetoacetoxyethyl methacrylate to the reactor at 1.72 g / min. Five minutes after the feeds are completed, a solution of the initiator composed of 0.4 g of sodium persulfate and 0.4 g of sodium metabisulfite dissolved in 12 g of water is added to the reactor and the heating is continued for 30 minutes. The latex is cooled, and 13.4 g of ammonium hydroxide (29%) is pumped into the latex. The latex is then filtered through a 100 mesh wire mesh. The latex is characterized as follows: solids level, 41.6; amount of dry material (100 mesh screen), 0.55 g; particle size (D), 58 nm; Tg of the polymer (as determined by differential scanning calorimeter, DSC), 8 ° C. Example 2 Preparation of particles transported in water containing small unsaturated acetoacetoxy (the latex particles contain 13.6% MAAE, oxygen content: 16.9).

To a 1,000 ml resin reactor equipped with a condenser, nitrogen purge, and subsurface feed tube 340 g of water, 15.52 g of HITENOL HS-20, 2.55 g of TERGITOL NP-40 surfactant (70% by weight) are added. in water), 3.5 g of sodium carbonate, 3.58 g of styrene, 11.64 g of 2-ethylhexyl acrylate, and 2.68 g of acetoacetoxyethyl methacrylate. A nitrogen purge is started, after which the reactor contents are brought to 80 ° C at 400 rpm. After Upon reaching 80 ° C, a solution of the initiator composed of 2.3 g of sodium persulfate dissolved in 13.0 g of water in the reactor is fed. An initiator solution composed of 1.3 g of sodium persulfate dissolved in 34 g of water in the reactor is fed at 0.16 g / min. Ten minutes after the feeding is started, an emulsion feed composed of 120 g of water, 6.55 g of surfactant AEROSOL 18 (anhydrous N-octadecyl sulfosuccinamate surfactant, available from Cytec Industries, Ine), 10.22 g TERGITOL NP-40 (70% by weight in water), 68.02 g of styrene (EST), 221.06 g of 2-ethylhexyl acrylate (2AEH), and 51.02 g of acetoacetoxyethyl methacrylate to the reactor at 1.72 g / min. Five minutes after the feeds are completed, a solution of the initiator composed of 0.4 g of sodium persulfate and 0.4 g of sodium metabisulfite digested in 12 g of water is added to the reactor and the heating is continued for 30 minutes. The latex is cooled, and 16.8 g of ammonium hydroxide (28%) is pumped into the latex. The latex is then filtered through a 100 mesh wire mesh. The latex is characterized as follows: solids level, 41.1; amount of dry material (100 mesh screen), 1.58 g; particle size (D), 58 nm; Tg of the polymer, -36 ° C. Example 2 Preparation of particles transported in water containing small unstructured acetoacetoxy "(the particles of latex contain 10.9% methacrylate MAAE; oxygen content: 202.3%). To a 1,000 ml resin reactor equipped with a condenser, nitrogen purge, and subsurface feed tube 340 g of water, 15.52 g of HITENSOL HS-20, 2.55 g of TERGITOL NP-40 surfactant (70% by weight) are added. in water), 3.5 g of sodium carbonate, 3.40 g of methyl methacrylate (MAM), 5.37 g of styrene (EST), 6.98 g of butyl acrylate (AB), and 2.15 g of acetoacetoxyethyl methacrylate (MAAE). A nitrogen purge is started, then the reactor contents are brought to 80 ° C at 400 rpm. After reaching 80 ° C, an initiator solution composed of 2.3 g of sodium persulfats dissolved in 13. Q g of water in the reactor is fed. An initiator solution composed of 1.3 g of sodium persulfate dissolved in 34 g of water in the reactor is fed at 0.16 g / min. After 10 minutes of starting the feed of the initiator, a monomer emulsion feed composed of 120 g of water, 6.55 g of AEROSOL 18, 10.22 g of TERGITOL NP-40 (70% by weight in water) is fed, 64.62 g of methyl methacrylate, 102.03 g of styrene, 132.64 g of butyl acrylate, and 40.81 g of acetoacetoxyethyl methacrylate to the reactor at 1.72 g / min. Five minutes after the feeds are completed, a solution of the initiator composed of 0.4 g of sodium persulfate and 0.4 g of sodium metabisulfite is added. in 12 g of water to the reactor and the heating is continued for 30 minutes. The latex is cooled, and 13.4 g of ammonium hydroxide (28%) is pumped into the latex. The latex is then filtered through a 100 mesh wire mesh. The latex is characterized as follows: solids level, 41.0; amount of dry material (100 mesh screen), 0.17 g; particle size (D), 57 nm; Tg of the polymer, 1.4 ° C. E-i emplo 4 - Preparation of particles transported in water containing small unstructured acetoacetoxy (latex particles contain 10.9% MAAE, oxygen content: 26.7%).

To a 1,000 ml resin reactor equipped with a condenser, nitrogen purge and subsurface feed pipe 340 g of water, 15.52 g of HITENOL HS-20, 2.55 g of TERGITOL NP-40 surfactant (70% by weight) are added. ), 3.5 g of sodium carbonate, 6.98 g of methyl methacrylate, 1.79 g of styrene, 6.98 g of butyl acrylate, and 2.15 g of acetoacetoxyethyl methacrylate. A nitrogen purge is started, then the reactor contents are brought to 80 ° C at 400 rpm. After reaching 80 ° C, a solution of the initiator composed of 2.3 g of sodium persulfate dissolved in 13.0 g of water in the reactor is fed. An initiator solution composed of 1.3 g of sodium persulfate dissolved in 34 g of water in the reactor is fed at 0.16 g / min. After 10 minutes of starting the feeding of the initiator, the feed an emulsion feed consisting of 120 g of water, 6.55 g of AEROSOL 18, 10.22 g of TERGITOL NP-40 (70% by weight), 132.64 g of methyl methacrylate, 34.01 g of styrene, 132.64 g of butyl acrylate , and 40.81 g of acetoacetoxyethyl methacrylate to the reactor at 1.72 g / min. Five minutes after the feeds are completed, a solution of the initiator composed of 0.4 g of sodium persulfate and 0.4 g of sodium metabisulfite dissolved in 12 g of water is added to the reactor and the heating is continued for 30 minutes. The latex is cooled, and 13.4 g of ammonium hydroxide (28%) is pumped into the latex. The latex is then filtered through a 100 mesh wire mesh. The latex is characterized as follows: solids level, 41.0; amount of dry material (100 mesh screen), 0.14 g; particle size (Dw), 57 nm; Tg of the polymer, 2 ° C. Example 5 comparative example - Latex E2950 of enamine available from Rohm and Haas. This latex is analyzed by elemental analysis and found to have an oxygen content of 29.8%. Evaluation of the enamine To 100 g of each of the above latexes are added with agitation 2 to 4 g of water, 1.2 g of TERGITQL NP-40, and 1.2 g of AEROSOL 18. The latex is then kept in a water bath Thermostatic at 50 ° or 60 ° C. To measure the functionality of the enamine that remains in the particles transported in water, the latex films are melted in ZnSe, air-dried for 15 minutes, then vacuum-dried for 15 minutes. Using infrared spectroscopy, the relative magnitude of the absorption of the enamine is determined by dividing the absorption of the enamine band at 1.568 cm "1 by the styrene band at 1.602 cm" 1. The latexes are usually conditioned at temperature for at least one day to ensure complete reaction of the ammonia with portions of acetoacetoxy to form the enamine. The decomposition tables are prepared for each latex at 50 ° C and 60 ° C. EXAMPLE 6 Preparation of Large Unsaturated Acetoacetoxy-Contained Water-Transported Particles for Hydrolytic Stability Studies A 295 g water, 1-4 ml, reactor-equipped condenser, nitrogen purge, and subsurface feed tube are added to a 1,000 ml resin reactor. 34 g of TREM LF-40, 1.79 g TERGITOL NP-40 (100%), 2,044 g of sodium carbonate, and 0.01 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water), and 17.9 g of monomer loading as shown in Table I below. A nitrogen purge is started, then the reactor contents are brought to 80 ° C at 400 rpm. After reaching 80 ° C, a solution of the initiator composed of 2.3 g of sodium persulfate dissolved in 13. Q g of water in the reactor is fed. An initiator solution is fed composed of 1.3 g of sodium persulfate dissolved in 34 g of water in the reactor at 0.16 g / min. After 10 minutes of starting the feed of the initiator, an emulsion feed composed of 120 g of water, 9.94 g of AEROSOL 18, 7.16 g of TERGITOL NP-40 (100% a), 341.1 g of charge is fed. of monomer, and 0.52 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% in water), to the reactor at 1.72 g / min. Five_ minutes after the feeds are completed, a solution of the initiator composed of 0.4 g of sodium persulfate and 0.4 g of sodium metabisulfite dissolved in 12 g of water is added to the reactox and the heating is continued for 30 minutes. The latex is then filtered through a 100 mesh wire mesh. Solids level, 42.6; amount of dry material (100 mesh screen), 0.20 g; particle size (Dw), 153 nm; Tg of the polymer, 14 ° C. Examples 7-9 Preparation of transported particles in water based on MAAE of variant oxygen content. The latexes are prepared essentially as described in Example 6 except that Example 7 uses less water to obtain concentrated solids. The composition of the monomer and characterization of each latex are shown in Tables I and II.

Table I percent of monomers used in the polymerization EST = styrene MAM = methyl methacrylate 2AEH = 2-ethylhexyl acrylate AB = butyl acrylate - MAAE = acetoacetoxyethyl methacrylate Table II Example 10 Hydrolytic stability studies of Examples 6 to 9 Latexes are aged in a thermostatic bath 50 ° C, 60 ° C, 70 ° C and 80 ° C and wet samples for films obtained as a function of time. The movies merge in crystals of ZnSe, and the absorption is determined at 1655 cm "1 (which is the characteristic of carbonyl absorption after the formation of enol) and the absorption of styrene at 1606 cm" 1. The film is normalized using styrene absorption and the decrease in enol absorption is calculated. The first-order proportion graphs are obtained, and the Arrhenius proportion graphs for each latex. S & use these graphs to calculate the free energy of the activation shown in Table III. The activation free energy is used to calculate the contour plots for 10% hydrolysis of the acetoacetoxy moiety as a function of the oxygen content in the particles transported in water, their storage time and temperature. The results are shown in Figure 4. Table III Example 11 - - Preparation of particles transported in water of unstructured small carbonate-containing vinyl ester (oxygen content 25.5%, VAM / VEOVA-10 / VEOVA- / VEC; 20/70/5/5) They are added to a 1,000 ml resin reactor equipped with a condenser, nitrogen purge, and subsurface feed tube 435.6 g of _agúa, 13.8 g of sodium vinylsulfonate, 11.43 g of TERGITOL NP-40 (70%), 1.0 g of sodium carbonate, 40 g of a monomer solution composed of 80 g of vinyl acetate, 280 g of VEOVA-10, 20 g of VEOVA-5, and 20 g of vinyl ethylene carbonate. A purge of nitrogen is started, then the contents of the reactor up to 65 ° C at 400 rpm. After reaching 65 ° C, an initiator charge composed of 1.03 g t-butyl hydroperoxide (70%) and 0.72 g of dissolved sodium formaldehyde sulfoxylate is added to the reactor. After five minutes the remaining monomer solution is fed into the 200 minutes, an initiator solution composed of 2.4 t-butyl hydroperoxide dissolved in 80 g of water is fed, and 1. 68 g of sodium formaldehyde sulfoxylate dissolved in 80 g in the reactor in 200 minutes. Fifteen minutes after the initiator solutions are completed, the reactor is cooled to 40 ° C. Sequentially post initiators and a catalyst composed of isoascorbic acid are charged a solution of 1% iron sulphate (0.53 g) to the reactor and heating is continued for 30 minutes. Solids 383.7%, dry solids "filterable (100 mesh sieve), 3.2 g, pH, 4.64; particle, 225 nm (Electron Micrographs); IR (absorption of carbonate), 1815 cm "1. Example 12 Preparation of particles transported in water of this - acrylic vinyl containing small unstructured carbonate (32.6% oxygen content, VAM / VEOVA-10 / AB / VEC; 65/10/20 / 5) They are added to a 1,000 ml resin reactor equipped with a condenser, nitrogen purge, and subsurface feed tube 435.6 -g water, 13.8 g sodium vinyl sulfonate, 11.43 g TERGITOL NP-40 (70%) , 1.0 g of sodium carbonate, 40 g of a monomer solution composed of 280 g of vinyl acetate, 40 g of VEOVA-10, 80 g of butyl acrylate, and 20 g of vinyl ethylene carbonate. of nitrogen, then bring the contents of the reactor up to 65 ° C at 400 rpm.After reaching 65 ° C, add a charge of the initiator composed of 1.03 g t-butyl hydroperoxide (70% aqueous solution) and 0.72 g of Sodium formaldehyde sulfoxylate dissolved in the reactor After five minutes the solution is fed remaining monomer in 200 minutes, fed an initiator solution composed of 2.4 t-butyl hydroperoxide dissolved in 80 g of water, and 1.68 g of sodium formaldehyde sulfoxylate dissolved in 80 g in the reactor in 200 minutes. Fifteen minutes after the initiator solutions are completed, the reactor is cooled to 40 ° C. Sequentially post initiators are loaded and a catalyst composed of isoascdric acid (0.53 g) and t-butyl hydroperoxide (0.53 g, 70% aqueous solution), and 1% iron sulphate solution (0.53 g) to the reactor and heating is continued for 30 minutes. Solids 38.7%, 5 filterable dry solids (100 mesh sieve), 3.2 g, pH, 4.64; particle size, 150 nm (Electron Micrographs); IR (carbonate absorption), 1815 cm "1. Example 13 Hydrolytic stability studies of examples 10 11 and 12 The latexes are aged in a thermostatic bath 50 ° C, 60 ° C, 70 ° C and 80 ° C and wet samples are obtained for films as a function of time. The films are melted on ZnSe crystals, and the absorption is determined at 1815 cm " 1 and the absorption of styrene at 1606 cm-1. The thickness of the film is normalized using the styrene absorption and the decrease in carbonate absorption is calculated. The data obtained from the hydrolysis of the carbonate portions are plotted as the natural log (Ing) of the absorption of Initial carbonate divided by carbonate absorption as a function of time. Example 14 Preparation of Small Unstructured Ephedra Containing Waterborne Particles 25 Add to a 1,000 ml resin reactor equipped with a condenser, nitrogen purge, and subsurface feed tube 351 g of water, 0.716 g of AEROSOL OT-75, 5.11 g of TERGITOL NP-40 (70%), 2.05 g of sodium carbonate, 3.58 g of methacrylate of methyl, 11.63 g of 2-ethylhexyl acrylate, 2.68 g of glycidyl methacrylate, and 0.014 g of 2-acrylamido-2-methylpropanesulfonate. A nitrogen purge is started, then the reactor contents are brought up to 80 ° C at 400"rpm After reaching 80 ° C, an initiator charge composed of 2.30 g of sodium persulfate dissolved in 13.0 g of water is added. The monomer feed, composed of 4.10 g of AEROSOL OT-75, 68.02 g of methyl methacrylate, 221.96 g of 2-ethylhexylacrylate or, 51.01 g of glycidyl methacrylate, and 0.26 g of sodium salt, is initiated. 2-acrylamido-2-methylpropanesulfonate sodium at 1.72 g / min Five minutes after the first emulsion feed is started, a solution of the initiator composed of 1.3 g of sodium persulfate dissolved in 33.5 g of water at 0.16 is fed. After five minutes after the feeding of the monomer emulsion is complete, a solution of the post-initiator of 0.4 g of sodium persulfate and 0.4 g of sodium metabisulfite dissolved in 12 g of water is loaded and the heating for 30 minutes. the emulsion, then the latex is filtered through a wire mesh screen 100. Solids level, 46.8; amount of the dried material (100 mesh screen), 8.93 g; pH, 8.2; he infrared analysis of clear films in ZnSe shows an absorption of epididium at 910 cm "1, - oxygen content, 22.7% Example 15 Preparation of particles transported in water containing small unstructured epidium They are added to a resin reactor of 1,000 ml equipped with a condenser, nitrogen purge, and subsurface feed tube 290 g of water, 1.34 g of TREM JF-40, 1.79 g of TERGITOL NP-40 (70%), 2.05 g of sodium carbonate, 33.58 g of methyl methacrylate, 11.63 g of butyl acrylate, 2.68 g of glycidyl methacrylate, and 0.010 g of 2-acrylamido-2-methylpropanesulfonate A nitrogen purge is initiated, then the reactor contents are brought to 80 ° C to 400 After reaching 80 ° C, a charge of the initiator composed of 2.30 g of sodium persulphate dissolved in 13.0 g of water is added to the reactor.The feed of the compound emulsion is started with 120 g of water, 9.94 g of AEROSOL 18, 7.16 of TERGITOL NP-40 (70% ), 68.02 g of methyl methacrylate, 221.96 g of butyl acrylate, 51.01 g of glycidyl methacrylate, and 0.26 g of sodium salt of 2-acrylamido-2-methylpropanesulfonate at 1.72 g / min. Five minutes after the first emulsion feed is started, a solution of the initiator composed of 1.3 g of "sodium persulfate dissolved in 33.5 g of water at 0.16 g / min. Is fed in. Five minutes after the feed is complete. the monomer emulsion, a post-initiator solution of 0.4 g of sodium persulfate and 0.4 g of sodium metabisulfite dissolved in 12 g of water is charged and the heating is continued for 30 minutes. The emulsion is cooled, then the latex is filtered through a 100 mesh wire screen. Solids level, 43.6; amount of dry material (100 mesh screen), 0.14 g; pH, 8.5; particle size 161 nm; infrared analysis of clear films in ZnSe shows an absorption of epoxide at 910 cm "1, oxygen content, 27.7% K-Example 16 Evaluations of examples 14 and 15 It is added to 100 g of latex 1.29" g of AEROSOL 18, 1.29 g of TERGITOL NP-40 (70%), and water to adjust the final solids to 40%. The latexes are then placed in a thermally controlled bath at 70 and 80 ° C. For analysis, small aliquots of the sample latex are taken in heated baths, and the films are melted in ZnSe. The absorption of epididium at 910 cm "1 is used to quantify the level of the epididium, as shown in Figures 8 and 9. Figure 10 shows the Arrhenius proportion graphs for hydrolysis. of the epididy portion in Examples 14 and 15. Obviously, numerous modifications and variations of the present invention are possible in the light of the foregoing teachings.

Within the scope of the appended claims, the invention may be practiced differently than as specifically described herein.

Claims

REIVXMPIGACIQMBS 1. A functional latex polymer composition, characterized in that it comprises: A vinyl polymer of copolymerizable monoethylenically unsaturated monomers wherein at least one monomer contains at least one large hydrolyzable functional portion; Wherein the combined oxygen and nitrogen content of the copolymerizable monoethylenically unsaturated monomers is up to about 27% by weight, based on the total weight of the copolymerizable monoethylenically unsaturated monomers; and wherein the vinyl polymer is resistant to hydrolysis.
2. The functional latex polymer composition according to claim 1, characterized in that the monomer containing at least one large hydrolysable functional portion is present in an amount of 3 to 30% by weight, based on the total weight of the monoethylenically monomers unsaturated copolymerizable.
3. The functional latex polymer composition according to claim 1, characterized in that the monomer which "contains at least one large hydrolysable functional portion is present in an amount of 12 to 15% by weight, based on the total weight of the the copolymerizable monoethylenically unsaturated monomers
4. The functional latex polymer composition of according to claim 1, characterized in that the large hydrolyzable functional portion is selected from the group consisting of the acetoacetoxy group, carbonate group, epoxide group and isocyanate group.
5. The latex polymer composition -functional according to claim 4, characterized in that the combined oxygen and nitrogen content is up to about 20% by weight based on the total weight of the copolymerizable monoethylenically unsaturated monomers.
6. The functional latex polymer composition according to claim 4, characterized in that the combined oxygen and nitrogen content is up to about 10% by weight based on the total weight of the copolymerizable monoethylenically unsaturated monomers.
7. The functional latex polymer composition according to claim 4, characterized in that the acetoacetoxy group is converted to an enamine group by reaction with ammonia or a primary amine capable of enamine formation.
8. The functional latex polymer composition according to claim 7, characterized in that the oxygen and nitrogen content is up to about 20% by weight, based on the total weight of the copolymerizable monoethylenically unsaturated monomers; and wherein the enamine group remains substantially non-hydrolyzed after from 1500 to 50 ° C.
9. The functional latex polymer composition according to claim 7, characterized in that the combined oxygen and nitrogen content is up to about 10% by weight, based on the total weight of the copolymerizable monoethylenically unsaturated monomers; and wherein the enamine group remains substantially non-hydrolyzed after 1500 hours at 50 ° C.
A method for producing a functional latex polymer, characterized in that it comprises: forming an aqueous monomer mixture comprising monoethylenically unsaturated monomers "copolymerizable at least one of which contains at least one large hydrolysable functional portion, wherein the combined oxygen and nitrogen content of the monomer mixture is in the range of up to about 27% by weight, based on the total weight of the monomer mixture; adjust the temperature of the monomer mixture to a level of 55 ° C at 90 ° C and Polymerize the monomer mixture to form a functional latex polymer composition resistant to hydrolysis 11.
The method according to claim 10, characterized in that the large hydrolyzable functional portion is selected from the group consisting of of the group acetoacetoxy, carbonate group, epoxy group and isocyanate group.
The method according to claim 10, characterized in that the combined oxygen and nitrogen content is adjusted to a level of up to about 20% by weight based on the total weight of the monomer mixture.
13. The method according to the claim 10, characterized in that the combined oxygen and nitrogen content is adjusted to a level of up to about 10% by weight based on the total weight of the monomer mixture
14. The method according to claim 11, characterized in that it further comprises converting the acetoacetoxy group to a large enamine group by reaction with a molar excess of ammonia or a primary amine capable of enamine formation.
15. The method of compliance with the claim 14, characterized in that the combined oxygen and nitrogen content is adjusted to a level of up to about 20% by weight based on the total weight of the monomer mixture; and wherein the enamine group remains substantially unhydrolyzed after 1500 hours at 50 ° C.
16. the method according to claim 14, characterized in that the combined oxygen and nitrogen content is adjusted to a level of up to about 10% by weight based on the total weight of the monomer mixture; and wherein the enamine group remains substantially unhydrolyzed after 1500 hours at 50 ° C.
17. The functional latex polymer composition according to claim 1, characterized in that the monomer containing at least one large hydrolysable functional portion is acetoacetoxyethyl (meth) acrylate.
18. The functional latex polymer composition according to claim 1, characterized in that the monomer containing at least one large hydrolyzable functional portion is selected from the group consisting of CH2 = CH-0-C (0) -C ( CH3) 3, CH2 = CH-0-C (O) -CH (C-OH) (C4H9), and CH2 = CH-0-C (0) -CH2CH3.
19. The functional latex polymer composition according to claim 1, characterized in that the monomer containing at least one large hydrolyzable functional portion is selected from the group consisting of glycidyl (meth) acrylate, allyl glycidyl ester, CH = CH
20. The functional latex composition according to claim 1, characterized in that the monomer containing at least one large hydrolyzable functional portion is m-isopropenyl-, a-dimethylbenzyl isocyanate. M