Polymerizable surfactants with water whitening resistance and methods of using the same

Abstract

Ethylenically unsaturated salts of allyl (poly)ether sulfates are disclosed for use as reactive surfactants or emulsifiers in emulsion polymerization processes.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 62 / 842,806, filed on May 3, 2019. Field of the Invention

[0003] This invention relates to polymerizable surfactants useful in preparing polymers by emulsion polymerization. Background Art

[0004] Surfactant is used in the multiple application for example dispersion, emulsification, wetting and foaming, and these applications span many industries, such as coating, adhesive, home care, personal care, building, paper, ink and the like.Surfactant is often included in products such as painting and coating, because these surfactants are necessary for stabilizing these products or in the manufacturing process of products.But, often, the existence of surfactant in finished product negatively affects the characteristic of hope in such finished product.In painting, for example, the existence of too much surfactant may contribute to the water sensitivity and water whitening of increase.

[0005] Emulsifiers are surfactants used to prepare polymers by a process known as emulsion polymerization. Typically, such emulsifiers are understood to affect the mechanical and chemical stability of the resulting emulsion. Further, emulsifiers play a role in the physical properties of the emulsion, such as viscosity, particle size, and the like. Emulsifiers also play a role in the physical properties of the film, such as weatherability, durability, and adhesion.

[0006] The latex produced is typically used in coating applications such as paint, ink, colorant, pressure sensitive adhesive ("PSA"), etc. Once the latex-containing product has been applied to a surface as part of a protective or decorative coating, the surfactant is no longer needed or desired. The presence of surfactants often degrades the moisture sensitivity of the coating. In addition, other coating properties, such as adhesion to the substrate surface, may be negatively affected. It is typically understood that this negative effect is largely due to the mobility of the surfactant polymer. For example, local high concentrations of surfactant molecules can be formed in the coating by the aggregation of micelle spheres coated with surfactants. When the coating is exposed to water, these unbound surfactant molecules can be extracted from the coating, leaving weak points or paths on the substrate surface. This may lead to pinhole effects and water erosion of the substrate. Other undesirable effects include whitening, blooming, or blushing in the coating film, which occurs due to contacting the film with water, causing the surfactant to migrate to the surface. As a result, the film may become turbid or whitened, and the film may lose its original gloss. Summary of the invention

[0007] These problems are believed to be due to the fact that the surfactants remain in the polymers as free forms. One method for reducing the content of such free surfactants is to react such surfactants with the polymers during the polymerization process or otherwise make them so that such surfactants are not retained in the product or intermediates in free form, i.e., reactive surfactants or "polymerizable surfactants". It should be understood that the terms "one or more reactive surfactants" and "one or more polymerizable surfactants" are used interchangeably herein.

[0008] In one aspect, described herein are reactive or polymerizable surfactants having formula (I):

[0009]

[0010] Where R1 is H, C8-C 14 Alkyl, bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl, wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5, and the bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] The heptenyl group may be optionally substituted on one or more ring carbon atoms with one or more (C1-C6)alkyl groups (otherwise referred to herein as "Nopol");

[0011] "x" is an integer from 1-5 and "y" is an integer from 5-15; and

[0012] M+ is, but is not limited to, H+, Na+, NH4+, K+ or Li+.

[0013] In another embodiment, R1 is H, a group according to formula (II) (otherwise referred to herein as "Nopol"), or a linear or branched: C1-C 50 Alkyl, C1-C 40 Alkyl, C2-C 30 Alkyl, C4-C 20 Alkyl, C6-C 20 Alkyl, C8-C 14 Alkyl, or C6-C 18 In another embodiment, "x" is an integer from 1-20 and "y" is an integer from 1-50, provided that x+y is greater than or equal to 1. In another embodiment, "x" is an integer from 0-40 and "y" is an integer from 0-40.

[0014] In yet another embodiment, M+ is H+, Na+, NH4+, K+ or Li+. In a preferred embodiment, M+ is Na+ or NH4+. In a more preferred embodiment, M+ is NH4+

[0015] In another aspect, methods are described herein for preparing polymers (including but not limited to latex polymer emulsions and paints) using reactive surfactants having formula (I) as emulsifiers. In another aspect, methods are described herein for preparing polymers (including but not limited to latex polymer emulsions and paints) using a polymerizable surfactant composition (or reactive surfactant composition) having formula (I) as an emulsifier in combination with at least one surfactant. In one embodiment, the surfactant is sodium alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl diphenyl oxide disulfonate, ethoxylated alkylphenol sulfate and phosphate, sulfate and phosphate of fatty alcohol. In another embodiment, the surfactant is C 10 -C 16 Alcohol ethoxylate sulfate or any salt thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A photograph of a paint (white and tinted with 5% colorant) of the invention's improvement compared to the prior art is shown.

[0017] Figure 2 Water whitening resistance and water resistance testing at room temperature are shown.

[0018] Figure 3 Water whitening resistance and water resistance tests at 90°C are shown.

[0019] Figure 4 The color ΔL values ​​of the water whiteness change (50 min at 90° C.) of the Examples are shown.

[0020] Figure 5 The colour ΔE values ​​of the water whiteness change (50 min at 90°C) of the Examples are shown.

[0021] Figure 6 The opacity (%) values ​​of the polymers (including Surfactant A and Surfactant B) in Table 6 are shown. DETAILED DESCRIPTION

[0022] In the Summary of the Invention and this Detailed Description, each numerical value should be read once as modified by the term "about" (unless expressly so modified), and then read again as not so modified unless the context dictates otherwise.

[0023] As used herein, the term "alkyl" means a saturated hydrocarbon group which may be linear, branched or cyclic, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, cyclohexyl.

[0024] As used herein, the term "cycloalkyl" means a saturated hydrocarbon group containing one or more cyclic alkyl rings, such as, for example, cyclopentyl, cyclooctyl, and adamantyl.

[0025] As used herein, the term "hydroxyalkyl" means an alkyl group, more typically an alkyl group, substituted by a hydroxy group, such as, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxydecyl.

[0026] As used herein, the term "alkylene" means a divalent acyclic saturated hydrocarbon group, including but not limited to methylene, polymethylene, and alkyl-substituted polymethylene such as, for example, dimethylene, tetramethylene, and 2-methyltrimethylene.

[0027] As used herein, the term "alkenyl" means an unsaturated straight chain, branched chain, or cyclic hydrocarbon group containing one or more carbon-carbon double bonds, such as, for example, ethenyl, 1-propenyl, 2-propenyl.

[0028] As used herein, the term "aryl" means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings, wherein the unsaturation may be represented by three conjugated double bonds, which may be substituted on one or more carbons of the ring by hydroxy, alkyl, alkenyl, halogen, haloalkyl or amino, such as, for example, phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl.

[0029] As used herein, the term "aralkyl" means an alkyl group substituted with one or more aryl groups, such as, for example, phenylmethyl, phenylethyl, triphenylmethyl.

[0030] As used herein, the term "(C n -C m )" (wherein n and m are each an integer) indicates that the group may contain from n to m carbon atoms per group.

[0031] As used herein, the term "ethylenic unsaturation" means a terminal (ie, for example, α, β) carbon-carbon double bond.

[0032] Emulsion polymerization is typically used in the preparation of aqueous latexes for use in coatings such as paints and inks. The polymerization reaction generally occurs in micelles in which the monomer droplets are stabilized by a surfactant. The surfactant is often an anionic surfactant in a mixture of anionic surfactants and nonionic surfactants under conditions that promote polymerization. These surfactants, together with the reaction conditions, determine the properties of the polymer such as particle size. For example, anionic surfactants can provide shear stability to prevent losses due to coagulation. Nonionic surfactants can provide electrolyte or chemical stability to growing latex particles. The type and structure of the surfactant may have a significant effect on emulsion properties such as particle size, particle size distribution and latex viscosity.

[0033] Like non-polymerizable surfactants, polymerizable surfactants are molecules that typically have a hydrophobic segment and an ionizable and / or polar group. The hydrophobic segment preferentially adsorbs onto the surface of polymer particles (e.g., latex polymer particles) during and after particle polymerization. The hydrophilic group extends into the aqueous phase and provides steric hindrance or charge repulsion that resists particle agglomeration and coagulation.

[0034] However, unlike their non-polymerizable counterparts, polymerizable surfactants additionally contain reactive groups on the hydrophobic segment that can covalently bind to the latex surface. Typically, this is a portion that can participate in free radical emulsion polymerization reactions, such as one or more terminal unsaturated carbon groups, such as vinyl or one or more olefin groups. When used in emulsion polymerization, a large portion of the surfactant molecules become irreversibly bound to the emulsion polymer chains and droplets. This can particularly improve latex stability and reduce foaming compared to other desired properties.

[0035] Polymerizable surfactants as described herein are prepared from readily available raw materials, and generally, their preparation does not require any equipment or special treatment.Polymerizable surfactants as described herein can be prepared in batch mode or continuous mode.These polymerizable surfactants can be prepared in various forms, including but not limited to liquid, solution, thin slice, powder, solid, semisolid, gel, annular gel or paste.In one embodiment, polymerizable surfactants are prepared in conventional solvents such as water, solvents (such as alcohol) or mixtures thereof, so as to produce an aqueous solution of polymerizable surfactants.In one embodiment, polymerizable surfactants as described herein also include surfactants in dry form as salts, and in another embodiment, polymerizable surfactants as described herein also include surfactants as aqueous solutions.The salt of polymerizable surfactants can be separated by drying the solution of polymerizable surfactants.The solution of polymerizable surfactants can be prepared by dissolving the salt of polymerizable surfactants in water, solvents or mixtures thereof.

[0036] The coating (comprising PSA) is obtained from an aqueous dispersion comprising an effective amount of a surfactant, the surfactant comprising at least one ionic polymerizable surfactant. The coating composed of at least one polymerizable surfactant exhibits better water whitening resistance in a hot water (90° C.) whitening test. In one embodiment, in particular, compared to a non-reactive conventional surfactant, C 12 / C 14 -2.6AGE-5EO-sulfate sodium salt, C 12 / C 14 -2.6AGE-15EO-sulfate sodium salt and nopol-2.6AGE-15EO-sulfate sodium salt exemplify improved resistance to hot water whitening. As used herein, "AGE" is allyl glycidyl ether.

[0037] In one embodiment, the sodium salt of nopol-2.6AGE-15EO-sulfate is represented as follows:

[0038]

[0039] wherein "x" is an integer from 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5; and "y" is an integer from 1-50, or 1-40, or 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5, or 3-50, or 3-40, or 3-30, or 3-25, or 3-20, or 3-15, or 3-10, or 3-5, or 5-50, or 5-40, or 5-30, or 5-25, or 5-20, or 5-15, or 5-10, or 5-7.

[0040] In one embodiment, in particular, compared to non-reactive conventional surfactants, C 12 / C 14 -2.6AGE-5EO-ammonium sulfate, C 12 / C 14 -2.6AGE-15EO-ammonium sulfate and nopol-2.6AGE-15EO-ammonium sulfate illustrate improved resistance to hot water whitening.

[0041] In one embodiment, nopol-2.6AGE-15EO-ammonium sulfate salt is represented as follows:

[0042]

[0043] wherein "x" is an integer from 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5; and "y" is an integer from 1-50, or 1-40, or 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5, or 3-50, or 3-40, or 3-30, or 3-25, or 3-20, or 3-15, or 3-10, or 3-5, or 5-50, or 5-40, or 5-30, or 5-25, or 5-20, or 5-15, or 5-10, or 5-7.

[0044] In one embodiment, C 12 / C 14 -2.6AGE-15EO-sodium sulfate is represented as follows:

[0045]

[0046] wherein "x" is an integer from 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5; and "y" is an integer from 1-50, or 1-40, or 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5, or 3-50, or 3-40, or 3-30, or 3-25, or 3-20, or 3-15, or 3-10, or 3-5, or 5-50, or 5-40, or 5-30, or 5-25, or 5-20, or 5-15, or 5-10, or 5-7.

[0047] In one embodiment, C 12 / C 14 -2.6AGE-15EO-sulfate ammonium salt is represented as follows:

[0048]

[0049] wherein "x" is an integer from 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5; and "y" is an integer from 1-50, or 1-40, or 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5, or 3-50, or 3-40, or 3-30, or 3-25, or 3-20, or 3-15, or 3-10, or 3-5, or 5-50, or 5-40, or 5-30, or 5-25, or 5-20, or 5-15, or 5-10, or 5-7.

[0050] The polymerizable surfactants described herein can be used in applications in which reactive surfactants containing one or more polyether groups have heretofore been used, in particular as emulsifiers for emulsion polymerization, dispersants for suspension polymerization, resin modifiers (for improving water repellency, adjusting hydrophilicity, improving antistatic properties, improving antifogging properties, improving water repellency, improving adhesion properties, improving dyeability, improving film-forming properties, improving weather resistance, improving anti-blocking properties, etc.), fiber processing aids, non-drip agents, soil resistance finishes, paints, and the like.

[0051] When any polymerizable surfactant as described herein is used as an emulsifier for emulsion polymerization, it can be used in any desired ratio within the range of ratios with other emulsifiers (surfactants) used for emulsion polymerization. In general, however, it can be preferably used in a ratio of from 0.1 to 20wt.%, typically in a ratio of from 0.2 to 10wt.%, and in other embodiments based on the one or more raw monomers in a ratio of from 0.2 to 5wt.%. In addition, in another embodiment, surfactants other than polymerizable surfactants as described herein can be used during the emulsion polymerization process. Non-reactive surfactants commonly used in emulsion polymerization processes include both anionic and non-ionic molecules. In one embodiment, reactive surfactants as described herein can be used with one or more anionic surfactants. In one embodiment, reactive surfactants as described herein can be used with one or more cationic surfactants. In one embodiment, reactive surfactants as described herein can be used with one or more nonionic surfactants. In one embodiment, reactive surfactants as described herein can use any combination of one or more anionic surfactants and one or more nonionic surfactants.

[0052] The anionic surfactants used in combination with the reactive surfactants as described herein (in the emulsion polymerization process) are as follows: sodium alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl diphenyl oxide disulfonate, ethoxylated alkylphenol sulfates and phosphates, fatty alcohol sulfates and phosphates, etc., or any salts thereof. The nonionic surfactants used in combination with the reactive surfactants as described herein (in the emulsion polymerization process) are as follows: alcohol ethoxylates, alkylphenol ethoxylates, etc., or any salts thereof. In one embodiment. The anionic surfactant is C 10-16 Alcohol ethoxylate sulfate or any salt thereof.

[0053] Although no particular limitation is imposed on the monomer or monomers to be subjected to emulsion polymerization, the polymerizable surfactant used for emulsion polymerization can be preferably used for acrylate emulsion, styrene emulsion, vinyl acetate emulsion, SBR (styrene / butadiene) emulsion, ABS (acrylonitrile / butadiene / styrene) emulsion, BR (butadiene) emulsion, IR (isoprene) emulsion, NBR (acrylonitrile / butadiene) emulsion and the like.

[0054] Suitable monomers that can be polymerized under the emulsion polymerization conditions described herein include ethylenically unsaturated monomers, such as vinyl monomers and acrylic monomers. Typical vinyl monomers suitable for use include, but are not limited to, vinyl esters, such as vinyl acetate, vinyl benzoate, vinyl propionate; vinyl aromatic hydrocarbons such as styrene, methyl styrene, other vinyl aromatic compounds, such as vinyl toluene, vinyl naphthalene, divinyl benzene, etc. Halogenated vinyl monomers, such as vinyl chloride, vinylidene chloride, etc., can also be used.

[0055] Suitable acrylic monomers typically include compounds with acrylic acid functionality, such as alkyl acrylates and methacrylates, acrylic acid and methacrylate acid, and acrylamide and acrylonitrile. Typical acrylic monomers include, but are not limited to, methyl acrylate and methyl methacrylate, ethyl acrylate and ethyl methacrylate, propyl acrylate and propyl methacrylate, and butyl acrylate and butyl methacrylate, benzyl acrylate and benzyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate, decyl acrylate and decyl methacrylate, and dodecyl acrylate and dodecyl methacrylate, etc. Other acrylic monomers include hydroxyalkyl acrylates and methacrylates such as hydroxypropyl acrylate and hydroxypropyl methacrylate and hydroxyethyl acrylate and hydroxyethyl methacrylate, acrylic acids such as methacrylic acid and acrylic acid, and amino acrylates and amino methacrylates.

[0056] Other examples of (co)polymerizable monomers in the acrylic emulsion may include (meth)acrylic acid (acrylate) alone, (meth)acrylic acid (acrylate) / styrene, (meth)acrylic acid (acrylate) / vinyl acetate, (meth)acrylic acid (acrylate) / acrylonitrile, (meth)acrylic acid (acrylate) / butadiene, (meth)acrylic acid (acrylate) / vinylidene chloride, (meth)acrylic acid (acrylate) / allylamine, (meth)acrylic acid (acrylate) / vinylpyridine, (meth)acrylic acid (acrylate) / alkylolamide, (meth)acrylic acid (acrylate) / N,N-dimethylaminoethyl ester, and (meth)acrylic acid (acrylate) / N,N-diethylaminoethyl vinyl ether.

[0057] Other additives or components known to those skilled in the art may also be used in accordance with the present invention. These include chain transfer agents to control molecular weight, additives to adjust pH, and compounds that act as protective colloids to provide additional stability to the latex particles.

[0058] In one embodiment, the polymerizable surfactant has formula (I):

[0059]

[0060] Where R1 is H or C8-C 14 alkyl; "x" is an integer from 1-5; "y" is an integer from 5-15; and M+ is H+, Na+, NH4+, K+ or Li+, preferably M+ is Na+ or NH4+. In certain embodiments, the polymerizable surfactant can be a mixture of two or more surfactants having formula (I), wherein R1 is two different C8-C 14 alkyl, and wherein "x" is an integer from 1-5; "y" is an integer from 5-15; and M+ is H+, Na+, NH4+, K+ or Li+, preferably M+ is Na+ or NH4+. For example, in certain embodiments, the polymerizable surfactant can be a mixture of two or more surfactants having formula (I), wherein at least one surfactant having formula (I) has R1, R1 is C8-C 14 Alkyl, preferably C 10 -C 14 alkyl, and wherein at least one different surfactant of formula (I) has R1, R1 is a different C8-C 14 Alkyl groups, preferably different C 10 -C 14 Alkyl, and wherein "x" is an integer from 1-5; "y" is an integer from 5-15; and M+ is H+, Na+, NH4+, K+ or Li+, preferably M+ is Na+ or NH4+.

[0061] In one embodiment, R1 is a bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl, wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5, and the bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] The heptenyl group may be optionally substituted on one or more ring carbon atoms with one or more (C1-C6)alkyl groups (otherwise referred to herein as "nopol").

[0062] In another embodiment, R1 is a bicyclic group, or more specifically in one embodiment a bicycloheptyl-polyether group, a bicycloheptyl-polyether group or a branched (C5-C 50)alkyl-polyether groups, wherein the bicycloheptyl-polyether groups or bicycloheptenyl-polyether groups may be optionally substituted on one or more ring carbon atoms by one or two (C1-C6)alkyl groups per carbon atom.

[0063] In one embodiment, R1 is a linear or branched chain: C1-C 50 Alkyl, C1-C 40 Alkyl, C2-C 30 Alkyl, C4-C 20 Alkyl, C6-C 20 Alkyl, C8-C 14 Alkyl, or C6-C 18 alkyl.

[0064] In another embodiment, "x" is an integer from 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5.

[0065] In another embodiment, "y" is an integer from 1-50, or 1-40, or 1-30, or 1-25, or 1-20, or 1-15, or 1-10, or 1-5, or 3-50, or 3-40, or 3-30, or 3-25, or 3-20, or 3-15, or 3-10, or 3-5, or 5-50, or 5-40, or 5-30, or 5-25, or 5-20, or 5-15, or 5-10, or 5-7.

[0066] In another embodiment, M+ is, but not limited to, H+, Na+, NH4+, K+ or Li+. In a preferred embodiment, M+ is Na+ or NH4+. In a more preferred embodiment, M+ is NH4+.

[0067] In another embodiment, R1 is a bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl, wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5, and the bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] The heptenyl group may be optionally substituted on one or more ring carbon atoms with one or more (C1-C6)alkyl groups.

[0068] More typically, R1 is:

[0069] (i) Double ring [3.1.1] Heptyl or bicyclic [3.1.1] heptenyl, which is bonded via its carbon atom at position 2 and is typically substituted on its carbon atom at position 6 by one or two (C1-C6)alkyl groups, more typically by two methyl groups, or

[0070] (ii) Double ring [3.1.1]Heptyl or bicyclic [2.2.1] Heptenyl, which is bonded via its carbon atom at position 2 or 3 and is typically substituted at its carbon atom at position 7 by one or two (C1-C6)alkyl groups, more typically by two methyl groups.

[0071] Suitable bicyclic groups include bicycloheptyl and bicycloheptenyl moieties, which may be derived, for example, from terpene compounds having a core (unsubstituted) 7 carbon atom bicyclic ring system according to structures (XII)-(XVII):

[0072]

[0073] For example, the bicycloheptenyl intermediate compound (II), also known as "nopol":

[0074]

[0075] is prepared by reacting β-pinene with formaldehyde, and

[0076] Bicycloheptyl intermediate compound (XIX) (referred to as "arbanol"):

[0077]

[0078] It is prepared by isomerizing α-pinene to camphene and ethoxylating the camphene.

[0079] In one embodiment, the bicycloheptyl intermediate or the bicycloheptenyl intermediate is alkoxylated by reacting the bicycloheptyl intermediate or the bicycloheptenyl intermediate with one or more oxirane compounds (such as ethylene oxide or propylene oxide) to form a bicycloheptyl-polyether intermediate or a bicycloheptenyl-polyether intermediate. The alkoxylation can be carried out according to well-known methods, typically at a temperature in the range of about 100° C. to about 250° C. and at a pressure in the range of from about 1 to about 4 bar in the presence of a catalyst such as a strong base, an aliphatic amine, or a Lewis acid and an inert gas such as nitrogen or argon.

[0080] Bicycloheptyl-polyether monomers or bicycloheptenyl-polyether monomers are then formed by adding polymerizable functional groups to the bicycloheptyl-polyether intermediate or bicycloheptenyl-polyether intermediate, for example by esterifying the bicycloheptyl-polyether intermediate or bicycloheptenyl-polyether intermediate with, for example, methacrylic anhydride under suitable reaction conditions.

[0081] In some embodiments, the sulfate group or phosphate group includes its corresponding salt form, wherein the cation includes but is not limited to Na+, NH4+, K+ or Li+.

[0082] In another embodiment, M+ is, but is not limited to, H+, Na+, NH4+, K+ or Li+. In a typical embodiment, M+ is Na+ or NH4+. In a preferred embodiment, M+ is NH4+.

[0083] The use of reactive surfactants as described herein in emulsion polymerization imparts to latex and / or coating applications at least one of the following benefits: bloom resistance, high temperature bloom resistance, moderate reactivity, PME stability, good process control, and excellent application properties (e.g., water sensitivity).

[0084] The polymerizable surfactant composition (or reactive surfactant composition) may comprise any reactive surfactant according to formula (I) as an emulsifier in combination with at least one surfactant. In one embodiment, the surfactant is sodium alkylbenzene sulfonate or any salt thereof, alkyl sulfosuccinate or any salt thereof, alkyl diphenyl oxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, sulfate and phosphate of fatty alcohol or any salt thereof. In another embodiment, the surfactant is alkyl alcohol ethoxylate sulfate or any salt thereof.

[0085] Examples

[0086] Preparation of polymerizable surfactants

[0087] Example 1. Polymerizable Surfactant C 12 C 14 -2.6 Preparation of AGE-15EO ammonium sulfate salt

[0088] 10.0 g of 45% potassium hydroxide solution was added to 320 g of Alfol 1214 and stirred at 80° C. in a reactor with a nitrogen subsurface purge. After heating to 100° C., the gas flow was stopped and the flask was evacuated by approximately 20" Hg using a vacuum pump. After one hour, the vacuum was broken with nitrogen and a sample was analyzed by Karl-Fischer titration, the moisture content was 0.09%.

[0089] 470.1 g of allyl glycidyl ether was added to the reactor over 120 minutes in the temperature range of 95°C-105°C. After 30 minutes, the reactor contents were heated to 120°C. After an additional six hours in the temperature range of 120°C-123°C, a sample of the reactor contents was titrated to naphthol benzyl alcohol indicator using 0.1 M perchloric acid in acetic acid and showed a basicity of 0.101 mmol / g in the presence of tetrabutylammonium bromide, indicating complete reaction of the added epoxide. 780 g of a clear liquid product was recovered from the reactor.

[0090] 360 g of the previously described adduct are charged to a stirred autoclave reactor and heated to 110° C. under a nitrogen subsurface purge. The reactor is evacuated to approximately 27″Hg and maintained under these conditions for 30 minutes. After breaking the vacuum with nitrogen and applying a positive nitrogen pressure of 1.1 bar, the reactor contents are heated to 155° C. and then 541 g of ethylene oxide are fed below the liquid surface between 155° C. and 156° C. over 140 minutes, reaching a maximum pressure of 5.3 bar. After one hour the pressure is released and the reactor contents are cooled to 115° C. and then purged again with nitrogen for 10 minutes and then discharged. 889 g of a clear liquid product are recovered from the reactor.

[0091] 647.3g of the previously described adduct is loaded into a 1 liter reactor, then stirred at 350RPM, bubbling of about 25ml / min nitrogen is started and heated to 65°C. Dicyandiamide (0.36g) is loaded into the reactor, then bubbled for 1 hour, to help reduce / remove dissolved oxygen, which helps color. 71.13g of sulfamic acid is loaded into the reactor in one hour, by dividing the charge into 5 almost equal additions. The reaction temperature is raised to 90°C, and it is maintained for 5 hours. The reaction mass is cooled to <40°C, and the dark amber liquid is bottled. The active matter % is determined by using the Hyamine test.

[0092] 1172.22 g of deionized water was charged to a two gallon open top reaction flask with a stainless steel turbine agitator. Agitation was started at 350 RPM. 18.5 g of 29% ammonium hydroxide was charged to the agitated water. 524.9 g of the previously described adduct with an active level of 100% tested by Hydrazine was slowly charged into the water in a steady stream while ensuring that the pH remained >7. Another 231 g of deionized water was charged to give a solution with an estimated 27% active. Agitation was maintained for 30 minutes. The clear amber liquid was bottled. The % active was determined to be 29.6%.

[0093] Example 2. Preparation of polymerizable surfactant Nopol-2.6AGE-15EO ammonium sulfate salt

[0094] 11.1 g of 45% potassium hydroxide solution was added to 283 g of nopol and stirred at 100° C. in a reactor with a nitrogen subsurface purge. The gas flow was stopped and the flask was evacuated to approximately 22" Hg using a vacuum pump. After one hour, the vacuum was broken with nitrogen and a sample was analyzed by Karl-Fischer titration, the water content was 0.06%.

[0095] 505.8 g of allyl glycidyl ether was added to the reactor over 120 minutes in the temperature range of 93° C. to 96° C. After 30 minutes, the reactor contents were heated to 120° C. After an additional five hours in the temperature range of 118° C. to 120° C., a sample of the reactor contents was titrated to naphthol benzyl alcohol indicator using 0.1 M perchloric acid in acetic acid and showed a basicity of 0.125 mmol / g in the presence of tetrabutylammonium bromide, indicating essentially complete reaction of the added epoxide (2 mol% residual epoxide = 98 mol% conversion of allyl glycidyl ether). 773 g of a clear liquid product was recovered from the reactor.

[0096] 351 g of the previously described adduct are charged to a stirred autoclave reactor and heated to 110° C. under a nitrogen subsurface purge. The reactor is evacuated to approximately 27″Hg and maintained under these conditions for 30 minutes. After breaking the vacuum with nitrogen and applying a positive nitrogen pressure of 1.0 bar, the reactor contents are heated to 155° C. and then 546 g of ethylene oxide are fed below the liquid surface between 155° C. and 156° C. over 130 minutes, reaching a maximum pressure of 5.6 bar. After one hour the pressure is released and the reactor contents are cooled to 110° C. and then purged again with nitrogen for 10 minutes and then discharged. 876 g of a clear liquid product are recovered from the reactor.

[0097] 691.4g of the previously described adduct is loaded into a 1 liter reactor, then stirred at 350RPM, bubbling of about 25ml / min nitrogen is started and heated to 65°C. Dicyandiamide (0.39g) is loaded into the reactor, then bubbled for 1 hour to help reduce / remove dissolved oxygen, which helps color. 84.65g of sulfamic acid is loaded into the reactor in one hour, by dividing the charge into 5 almost equal additions. The reaction temperature is raised to 90°C, and it is maintained for 5 hours. The reaction mass is cooled to <40°C and bottled. The active matter % is determined by using the Hydrazine test, and the active matter % is used to dilute to the desired 30%.

[0098] 1165.61 g of deionized water was charged to a two gallon open top reaction flask with a stainless steel turbine agitator. Agitation was started at 350 RPM. 16.0 g of 29% ammonium hydroxide was charged to the agitated water, resulting in a pH of 10.62. 529.5 g of the previously described adduct, which passed the Hydrazine test with an active level of 99.8%, was slowly charged to the water in a steady stream, while ensuring that the pH remained >7. Another 50.2 g of deionized water was charged to give a solution of approximately 30% actives. Agitation was maintained for 30 minutes. The clear amber liquid was bottled. The % actives was determined to be 30.5%.

[0099] Examples 3 to 9. The polymerizable surfactants AI in Examples 1-9 shown in Table 1 were prepared by following the procedure described in Example 1 while adjusting the molar ratios of the starting materials accordingly.

[0100] Table 1 - Polymerizable Surfactants in Examples 1-9

[0101] Examples Sample ID describe solid Example 1 Surfactant A <![CDATA[C 12-14 -2.6AGE-15EO-sulfate]]> 29.10％ Example 2 Surfactant B Nopol-2.6AGE-15EO-sulfate 29.27％ Example 3 Surfactant C <![CDATA[C 12-14 -1.3AGE-5EO-sulfate]]> 34.30％ Example 4 Surfactant D <![CDATA[C 12-14 -1.3AGE-10EO-sulfate]]> 31.89％ Example 5 Surfactant E <![CDATA[C 12-14 -1.3AGE-15EO-sulfate]]> 33.45％ Example 6 Surfactant F <![CDATA[C 12-14 -2.6AGE-5EO-sulfate]]> 33.23％ Example 7 Surfactant G <![CDATA[C 12-14 -2.6AGE-10EO-sulfate]]> 31.18％ Example 8 Surfactant H Nopol-2.6AGE-5EO-sulfate 29.87％ Example 9 Surfactant I Nopol-2.6AGE-10EO-sulfate 30.39％

[0102] Example 10. Preparation of latex polymer by using surfactant A in all-acrylic emulsion polymerization

[0103] Deionized water (230.0 g) and polymerizable surfactant A (29.10% solids, 3.2 g) were added to a suitable reactor for emulsion polymerization equipped with stirring, heating and cooling under a slow continuous nitrogen purge. The temperature of the reactor was raised to 80° C. with continuous stirring. At 80° C., a monomer pre-emulsion (26.07 g) [5.0% total pre-emulsion was prepared by mixing water (115 g) polymerizable surfactant A (5.8 g), methyl methacrylate (40 g), 2-ethylhexyl acrylate (296 g), acrylic acid (12 g), Sipomer BCEA (4 g) and chain transfer agent (0.5 g) and adjusted with ammonia (6.4 g)] was added to the reactor. Once the temperature of the reactor stabilized at 80° C. ammonium persulfate (0.5 g of a 5% solution dissolved in deionized water (10 g) was added to the reactor.

[0104] Twenty-five minutes later, a sample was taken out of the reactor for particle size analysis. The seed particle size was 79.5 nm. Five minutes later, the remaining monomer pre-emulsion and initiator solution (1 g, dissolved in 100 g deionized water) were added continuously at a temperature of 80°C for 3 hours. The addition of the monomer pre-emulsion was completed within 2 hours and 45 minutes. The initiator addition was completed within 3 hours. The reactor was further maintained at 80°C for 30 minutes until the final solid value was constant or close to the maximum theoretical value. The polymer dispersion obtained had a solid content of 44.51% and an average particle size of 137.9 d.nm. The reactor was cooled below 40°C and the resulting latex was filtered through a 200um polyester filter. The properties of the latex are given in Table 2.

[0105] Example 11. A latex polymer was prepared by following a similar procedure as described in Example 10 using the polymerizable surfactant samples prepared in Examples 2 to 9, and the latex formulation is set forth in Table 2.

[0106] Table 2. Formulation of latex polymer (in grams)

[0107]

[0108]

[0109] Comparative Example 12. Preparation of latex polymer by using comparative non-polymerizable surfactant.

[0110] The polymerization recipe is listed in Table 3, and the process is similar to that of Example 10. Conventional non-polymerizable surfactants RHODACAL DS-10 (sodium dodecylbenzene sulfonate, Comparative Sample A) and RHODAFAC PA12 (oleyl ether ethoxylated phosphate, Comparative Sample B) were used. The properties of the latex are listed in Table 4.

[0111] Table 3. Comparative surfactant formulations (in grams)

[0112]

[0113]

[0114] Table 4. Latex properties

[0115]

[0116] Example 13. Water whitening resistance and water resistance testing in pressure sensitive adhesive (PSA) applications.

[0117] The latex polymers prepared in Examples 10 to 12 were tested for water blooming resistance and water resistance performance in PSA applications. Water blooming resistance was measured at room temperature and elevated temperature water conditions (about 90°C).

[0118] The water whitening resistance test was conducted according to the following test method. The latex polymer was applied to the PET film using a 90 μm applicator and dried in a 110°C oven for 3 minutes. The film was allowed to cool overnight. The film was then immersed in a room temperature water bath for up to 24 hours and in an elevated temperature condition of 90°C for up to 50 minutes. Water whitening resistance and water resistance were tested on a 0 to 5 scale: 0 is the worst and 5 is the best. The measurement of water whitening was evaluated by examining the change in color ΔL value and ΔE value of the film before and after immersion in water. The test results are given in Figure 2-5 Given in.

[0119] Figure 2 Water whitening resistance and water resistance testing at room temperature are shown.

[0120] Figure 3 Water whitening resistance and water resistance tests at 90°C are shown.

[0121] Figure 4 The color ΔL values ​​of the water whiteness change (50 min at 90° C.) of the Examples are shown.

[0122] Figure 5 The colour ΔE values ​​of the water whiteness change (50 min at 90°C) of the Examples are shown.

[0123] Test data show that, compared with traditional surfactants, the polymerizable surfactant prepared by the present invention significantly improves the water whitening resistance and water resistance of latex polymers in pressure-sensitive adhesive applications.

[0124] Example 14. By using the polymerizable surfactant samples (Surfactant A and Surfactant B) prepared in Examples 1 and 2 in styrene-acrylic emulsion polymerization, latex polymers were prepared by following the procedure described below. Comparative surfactant samples, Comparative Sample C (sodium salt of allyl ethoxylated sulfate), Comparative Sample D (sodium salt of tristyrylphenol EO-PO sulfate), and Comparative Sample E (ammonium salt of tristyrylphenol EO phosphate) were also used to prepare latex polymers. The formulations of these latex polymers are given in Table 5.

[0125] Table 5 (in grams)

[0126]

[0127]

[0128] Deionized water (DI) (233.5 g) and sample surfactant A (8.3 g) were mixed and added to a suitable reactor for emulsion polymerization equipped with stirring, heating and cooling devices under a slow continuous nitrogen purge. The temperature of the reactor was raised to 80.0° C. under continuous stirring. A monomer pre-emulsion (28.3 g) [prepared by mixing deionized water (149.7 g), surfactant A (8.3 g), styrene (194 g), butyl acrylate (190 g), acrylic acid (10 g), acrylamide (6 g) and vinyltrimethoxysilane (2 g) to prepare a 5.0% total 560 g monomer pre-emulsion] was added to the reactor at 80.0° C. (the pre-emulsion was stabilized before addition), followed by the addition of ammonium persulfate (10.5 g) solution [ammonium persulfate (0.5 g) dissolved in deionized water (10 g)]

[0129] The seeds were kept for 15 minutes. A small sample was taken out to check the particle size. The continuous addition of the remaining monomer pre-emulsion (532.7 g) and the initiator solution [ammonium persulfate (1.50 g) dissolved in deionized water (70.0 g)] was set to be completed within 3 hours. The reactor was further kept at 80° C. for 30 minutes until the value of the final solid was constant or close to the maximum theoretical value. The reactor was then cooled below 40° C. and the resulting latex was filtered through a polyester filter. The polymer was neutralized to a pH of 8-8.5 using 28% ammonium hydroxide. The polymer dispersion obtained had a solids content of 44.3%, a viscosity of 1373 cP, and an average particle size of 119.2 d.nm. The following table gives the properties of the latex. Other polymers were also prepared according to a similar procedure, and their properties are also listed in Table 6.

[0130] Table 6

[0131]

[0132] The water whitening resistance and water resistance of the prepared polymers were tested by the flow method.

[0133] 1. Test samples were prepared with 3% Texanol (3 g Texanol / 100 g latex): MFFT was below 5 degrees Celsius.

[0134] 2. Clean the black glass plate with ethanol to ensure there is no contamination.

[0135] 3. Apply 120 um wet latex film on clean black glass plate, prepare each sample in duplicate.

[0136] 4. Store the black glass plate at room temperature for one day.

[0137] 5. Immerse the black glass plate in deionized water for 3 days.

[0138] 6. Remove the glass plate from the water and gently dry the film and glass with soft paper, making sure not to damage the latex film. Measure the opacity value immediately with a spectrophotometer.

[0139] The opacity value indicates the water whitening resistance and water resistance performance of the latex and the paint film. The smaller the opacity value shown, the less water whitening and therefore the better the water resistance. Figure 6 The opacity (%) values ​​of these polymers are shown, and samples Surfactant A and Surfactant B show better water whitening resistance and water resistance properties than the comparative sample.

[0140] Example 15. A latex polymer was prepared by following the procedure described in Example 14 using the polymerizable surfactant sample (Surfactant B) prepared in Example 2 in a styrene-acrylic emulsion polymerization. The formulation of the latex polymer is given in Table 7. A comparative surfactant sample, Comparative Sample E (tristyrylphenol EO ammonium phosphate), was also used to prepare a latex polymer.

[0141] Table 7 (in grams)

[0142]

[0143]

[0144] The properties of these polymers are listed in Table 8.

[0145] Table 8

[0146] characteristic Latex G Latex H Surfactants Surfactant B Comparative sample D Actual solids (%) 45.80％ 46.00％ pH 8.4 7.7 PS(nm) 92 100 Viscosity (RVF, 30rpm) 996 1180 MFFT(℃) 23 to 24 24

[0147] The latex polymers were formulated in 49% PVC exterior paints for use on stone or other architectural substrates. The paint formulations are given in Table 9.

[0148] Table 9

[0149]

[0150]

[0151] The watermark resistance and surfactant leaching properties of this formulated exterior paint were evaluated according to the following method. The results are reported on a scale from 1 to 10, with 1 being the worst and 10 being the best. The surfactants of the present invention significantly improved the watermark resistance and surfactant leaching properties of the paint.

[0152] 1. Apply 1 coat of paint (150μ-WFT) on the substrate and dry for 24-28 hours.

[0153] 2. Apply water drops on the painted film and allow the water drops to stay for 10 minutes.

[0154] 3. Lift the panel vertically and allow the water droplets to flow downward.

[0155] 4. Keep the panel in a vertical position and observe the watermark after drying.

[0156] Figure 1 Improved watermark resistance is shown for a white base paint, as well as a paint tinted with 5% colorant.

[0157] Claim of Invention

[0158] The following claims also describe features that the present invention may have.

[0159] Statement 1. A polymerizable surfactant composition comprising:

[0160] A polymerizable surfactant having formula (I):

[0161]

[0162] Where R1 is C8-C 14 Alkyl or bicyclic groups;

[0163] Where "x" is an integer from 1 to 20,

[0164] Where "y" is an integer from 1 to 30;

[0165] Among them, M + Yes H + 、Na + NH4 + , K + or Li + ;as well as

[0166] Optionally, at least one surfactant.

[0167] Statement 2. A polymerizable surfactant composition as described in statement 1, wherein M + Yes + or NH4+.

[0168] Statement 3. The polymerizable surfactant composition of statement 1 or 2, wherein "x" is an integer from 1-40, and wherein "y" is an integer from 1-50.

[0169] Statement 4. A polymerizable surfactant composition as described in any of Statements 1-3, further comprising a surfactant, which comprises any one of the following: sodium alkylbenzene sulfonate or any salt thereof, alkyl sulfosuccinate or any salt thereof, alkyl diphenyl oxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, fatty alcohol sulfate or any salt thereof, fatty alcohol phosphate or any salt thereof, alkyl alcohol ethoxylate sulfate or any salt thereof.

[0170] Statement 5. A polymerizable surfactant composition as described in any of the preceding statements, wherein R1 is a bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl, wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5, and the bicyclic [d.e.f] Heptyl or bicyclic [d.e.f]The heptenyl group may be optionally substituted on one or more ring carbon atoms with one or more (C1-C6)alkyl groups.

[0171] Statement 7. The polymerizable surfactant composition of any of the preceding statements wherein "y" is an integer from 5-15.

[0172] Statement 8. A method for preparing a coating comprising introducing a composition as described in any one of the preceding statements as an emulsifier during an emulsion polymerization process.

[0173] Statement 9. A polymerizable composition comprising:

[0174] A polymerizable surfactant having formula (I):

[0175]

[0176] Where R1 is C8-C 14 Alkyl or bicyclic groups;

[0177] Where "x" is an integer from 1 to 20;

[0178] Where "y" is an integer from 1 to 30;

[0179] Among them, M + Yes H + 、Na + NH4 + , K + or Li + ;as well as

[0180] one or more (co)polymerizable monomers, the one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers or vinyl ester monomers, and

[0181] Optionally, at least one surfactant.

[0182] Statement 10. The polymerizable composition of statement 9, wherein M + It is Na+ or NH4+.

[0183] Statement 11. The polymerizable composition of statement 9 or 10, wherein "x" is an integer from 1-40, and wherein "y" is an integer from 1-50.

[0184] Statement 12. A polymerizable surfactant composition as described in statement 9, 10 or 11, further comprising a surfactant, which comprises any one of the following: sodium alkylbenzene sulfonate or any salt thereof, alkyl sulfosuccinate or any salt thereof, alkyl diphenyl oxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, fatty alcohol sulfate or any salt thereof, fatty alcohol phosphate or any salt thereof.

[0185] Statement 13. A polymerizable composition as described in any of Statements 9-12, wherein R1 is a bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl, wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d+e+f=5, and the bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] The heptenyl group may be optionally substituted on one or more ring carbon atoms with one or more (C1-C6)alkyl groups.

[0186] Statement 14. The polymerizable composition of any of statements 9-13, wherein "x" is an integer from 1-5.

[0187] Statement 15. The polymerizable composition of any of statements 9-14, wherein "y" is an integer from 5-15.

[0188] Statement 16. The polymerizable surfactant composition of any of statements 1-8 or the polymerizable surfactant composition of any of statements 9-15, further comprising at least one ingredient selected from chain transfer agents, additives for adjusting pH, and compounds that function as protective colloids.

[0189] Statement 17. A pressure sensitive adhesive comprising the polymerizable surfactant composition of any of Statements 1-8.

[0190] Statement 18. The pressure sensitive adhesive of statement 17, wherein the pressure sensitive adhesive has improved water whitening resistance and water resistance properties relative to a polymerizable surfactant composition that does not contain the polymerizable surfactant having formula (I).

[0191] Statement 19. A pressure sensitive adhesive comprising the polymerizable composition of any of Statements 9-15.

[0192] Statement 20. The pressure sensitive adhesive of statement 19, wherein the pressure sensitive adhesive has improved water whitening resistance and water resistance properties relative to a polymerizable surfactant composition that does not contain the polymerizable surfactant having formula (I).

[0193] Statement 21. A paint having improved watermark resistance and surfactant leaching resistance properties comprising the polymerizable surfactant composition of any of Statements 1-8.

[0194] Statement 22. The paint of statement 21 further comprising an acrylic latex.

[0195] Statement 23. A process comprising polymerizing a mixture of a polymerizable polymer and the polymerizable surfactant composition of any of Statements 1-8 by emulsion polymerization.

[0196] Statement 24. A method comprising emulsion polymerizing the polymerizable composition of any of Statements 9-15 by emulsion polymerization.

[0197] Statement 25. A polymerizable surfactant composition comprising:

[0198] A polymerizable surfactant having formula (I):

[0199]

[0200] Where R1 is C8-C 14 Alkyl or bicyclic groups;

[0201] Where "x" is an integer from 1 to 20,

[0202] Where "y" is an integer from 1 to 30;

[0203] Among them, M + Yes H + 、Na + NH4 + , K + or Li + ;as well as

[0204] Optionally, at least one additional surfactant.

[0205] It is apparent that embodiments other than those expressly described herein are within the spirit and scope of the present claims. Accordingly, the present invention is not limited by the foregoing description, but is to be accorded the full scope of the claims so as to encompass any and all equivalent compositions and methods.

Claims

1. A polymerizable surfactant composition comprising: A polymerizable surfactant having formula (I): (I)， Where R1 is a bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl, wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d + e + f = 5, and the bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl is optionally substituted on one or more ring carbon atoms with one or more C1-C6 alkyl groups; Where "x" is an integer from 1 to 40, Where "y" is an integer from 1 to 50; Among them, M + Yes H + 、Na + NH4 + , K + or Li + ;as well as Optionally, at least one surfactant.

2. The polymerizable surfactant composition according to claim 1, wherein M + Yes + or NH4 + .

3. The polymerizable surfactant composition according to claim 1, wherein "x" is an integer from 1-20, and wherein "y" is an integer from 1-30.

4. The polymerizable surfactant composition of claim 1, further comprising a surfactant, the surfactant comprising any one of the following: sodium alkylbenzene sulfonate, alkyl sulfosuccinate or any salt thereof, alkyl diphenyl oxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, fatty alcohol sulfate or any salt thereof, fatty alcohol phosphate or any salt thereof, alkyl alcohol ethoxylate sulfate or any salt thereof.

5. The polymerizable surfactant composition according to claim 1, wherein "x" is an integer from 1-5.

6. The polymerizable surfactant composition according to claim 1, wherein "y" is an integer from 5-15.

7. The polymerizable surfactant composition of claim 1, further comprising at least one ingredient selected from the group consisting of a chain transfer agent, an additive for adjusting pH, and a compound serving as a protective colloid.

8. A method for preparing a coating, which comprises introducing the composition according to claim 1 as an emulsifier during emulsion polymerization.

9. A polymerizable composition comprising: A polymerizable surfactant having formula (I): (I)， Where R1 is a bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl, wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of d + e + f = 5, and the bicyclic [d.e.f] Heptyl or bicyclic [d.e.f] Heptenyl is optionally substituted on one or more ring carbon atoms with one or more C1-C6 alkyl groups; Where "x" is an integer from 1 to 40, Where "y" is an integer from 1 to 50; Among them, M + Yes H + 、Na + NH4 + , K + or Li + ;as well as one or more polymerizable monomers, the one or more polymerizable monomers comprising an acrylate monomer, a styrene monomer or a vinyl ester monomer, and Optionally, at least one surfactant.

10. The polymerizable composition of claim 9, wherein the polymerizable monomer is a copolymerizable monomer.

11. The polymerizable composition of claim 9, wherein M + Yes + or NH4 + .

12. The polymerizable composition of claim 9, wherein: "x" is an integer from 1-20, and wherein "y" is an integer from 1-30.

13. The polymerizable composition of claim 9, further comprising a surfactant, the surfactant comprising any one of the following: sodium alkylbenzene sulfonate, alkyl sulfosuccinate or any salt thereof, alkyl diphenyl oxide disulfonate or any salt thereof, ethoxylated alkylphenol sulfate or any salt thereof, ethoxylated alkylphenol phosphate or any salt thereof, fatty alcohol sulfate or any salt thereof, fatty alcohol phosphate or any salt thereof.

14. The polymerizable composition of claim 9, wherein: "x" is an integer from 1-5.

15. The polymerizable composition of claim 9, wherein: "y" is an integer from 5-15.

16. The polymerizable composition of claim 9, further comprising at least one ingredient selected from the group consisting of chain transfer agents, additives for adjusting pH, and compounds acting as protective colloids.

17. A pressure-sensitive adhesive having improved water-whitening resistance and water resistance properties, comprising a polymer obtained from the polymerizable surfactant composition of claim 1.

18. A pressure sensitive adhesive having improved water whitening resistance and water resistance properties, comprising a polymer obtained from the polymerizable composition of claim 9.

19. A paint having improved watermark resistance and surfactant leaching resistance properties comprising a polymer resulting from the polymerization of the polymerizable surfactant composition of claim 1.

20. A paint having improved watermark resistance and surfactant leaching resistance properties comprising a polymer resulting from the polymerization of the polymerizable composition of claim 9.

21. A paint according to claim 19 or 20 further comprising an acrylic latex.

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