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    • 专利摘要:
    The present invention provides about 20% to about 76% by weight fatty alcohol ethoxylate having an ethoxylation of at least 14; About 4% to about 40% alkylpolyglycoside; And from about 20% to about 60% by weight of water, wherein the surfactant composition is a liquid free of gel or solid phase at room temperature, a latiss containing the surfactant composition and a method of making the latiss.
    公开号:KR20000070738A
    申请号:KR1019997006988
    申请日:1998-02-02
    公开日:2000-11-25
    发明作者:루돌프 클리마；월리스 에이치. 피핀；마르시에 나탈리；토마스 알. 홉킨스；디에테르 포이슈텔；칭 펭
    申请人:웨인 씨. 제쉬크；헨켈 코포레이션；
    IPC主号:
    专利说明:

    Alkylpolyglycoside-containing surfactant composition for emulsion polymerization reaction {ALKYLPOLYGLYCOSIDE CONTAINING SURFACTANT BLENDS FOR EMULSIOIN POLYMERIZATION}
    The market for nonionic surfactants for emulsion polymerization is quite large (100 mm # / yr). Their main advantage over anionic surfactants is decreasing because they are water sensitive like paint. Most of DISPONILS (trade name; Henkel Corp., Ambler, Pennsylvania), which are ethoxylated fatty alcohols, are solids within a fairly large temperature range, making them difficult to use and their activity. Limit the concentration range. Alkyl phenol ethoxylates (APE) nonionic surfactants have been under scrutiny with the EPA as substances that cause physical and genetic defects in wildlife and as environmental hormones. There is a tendency to gradually move away from the APE. However, no government regulation adequately prohibits APE, so latex manufacturers require less costly non-ionics, resulting in environmentally desirable activities requiring conversion from APE.
    Thus, given the many requirements that polymer dispersions currently have to meet, new polymer emulsifiers continue to be required. In this regard, the emulsifiers used in the emulsion polymerization process have a decisive influence on the mechanical and chemical stability of the finished polymer emulsion (dispersion) and the final product as well as the initiation and subsequent process of the polymerization. As such, these properties of the emulsion and formulated product, such as freezing stability and storage stability, depend critically on the emulsifier.
    The present invention relates to combinations of alcohol ethoxylates with alkyl glycosides and methods of using them in emulsion polymerization of unsaturated monomers.
    1 is a ternary diagram of an alkylpolysaccharide (APS) -FAE-water composition.
    Figure 2 is a binary diagram of Disponil LS30 (lauryl alcohol 30-ethoxylate) as a control.
    3 is a binary diagram of disponyl LS30 (lauryl alcohol 30-ethoxylate), 60: 5 (% by weight of active substance) APS 220 with varying water (100%-% solids).
    4 is a binary diagram of disponyl LS30 (lauryl alcohol 30-ethoxylate), 55:10 (% by weight of active substance) APS 220 with varying water (100%-% solids).
    FIG. 5 is a binary diagram of disfonyl LS30 (lauryl alcohol 30-ethoxylate), 50:15 (% by weight of active substance) APS 220 with varying water (100%-% solids).
    FIG. 6 is a binary diagram of disponyl LS30 (lauryl alcohol 30-ethoxylate), 43:22 (% by weight of active substance) APS 220 with varying water (100%-% solids).
    FIG. 7 is a binary diagram of disponyl LS30 (lauryl alcohol 30-ethoxylate), 35:30 (% by weight of active substance) APS 220 with varying water (100%-% solids).
    8 is a binary diagram of APS 220 and water as a control.
    9 is a binary diagram of disonyl LS50 (lauryl alcohol 50-ethoxylate) and water as controls.
    FIG. 10 is a binary diagram of disfonyl LS50 (lauryl alcohol 50-ethoxylate), 55:10 (% by weight of active substance) APS 220 with varying water (100%-% solids).
    FIG. 11 is a binary diagram of disponyl LS50 (lauryl alcohol 50-ethoxylate), 45:20 (% by weight of active substance) APS 220 with varying water (100%-% solids).
    12 is a binary diagram of disponyl LS50 (lauryl alcohol 30-ethoxylate), 35:30 (% by weight of active substance) APS 220 with varying water (100%-% solids).
    FIG. 13 shows a binary diagram of TA 430 (trade name; Henkel Corporation, Tallow Alcohol 40-Ethoxylate), 50:30 (% by weight of active substance) APS 220 with varying water (100%-% solids). to be.
    FIG. 14 shows a binary diagram of TA 430 (trade name; Henkel Corporation, Tallow Alcohol 40-Ethoxylate), 40:36 (% by weight of active substance) APS 220 with varying water (100%-% solids). to be.
    Summary of the Invention
    The present invention provides about 20% to about 76% by weight of fatty alcohol ethoxylate (FAE), based on the total weight of fatty alcohol ethoxylate, alkylpolyglycoside and water, having an ethoxylation degree of 14 or more. A surfactant composition comprising from about 40 wt% to about 40 wt% alkylpolyglycoside and about 20 wt% to about 60 wt% water, a latice containing the surfactant composition and a process for preparing the latis The method relates to a process wherein said composition is a liquid free of gel or solid phase at room temperature. "Lattice" and "latexes" are used interchangeably herein.
    Detailed description of the invention
    Although the higher ethoxylated fatty alcohols of the present invention are solid at room temperature, certain tertiary mixtures of water-alkylpolysaccharides, such as alkylpolyglycoside-fatty alcohol ethoxylates (FAE), have a relatively high percentage of It was found to be a liquid with a solid. The liquid nature of these surfactant blends facilitates metering, mixing and dispensing. In addition, since certain compositions are commonly used when performing emulsion polymerization, such compositions do not form any gel when diluted in water. In addition, latexes made from the mixtures of the present invention exhibit low coagulation and good mechanical shear stability when using low levels of surfactants. Films produced by drying these latexes are preferred because they have low moisture absorption.
    In addition to the working examples, or where otherwise indicated, use herein All numbers expressing amounts of components and reaction conditions will be understood to be modified in all cases by the term "about." In addition, all percentages are by weight unless otherwise specified. Fatty alcohol ethoxylates will be mentioned first, followed by APS, followed by these surfactants, further surfactants and preferred combinations of APS / FAE blends or other ingredients that can be employed as latex containing them. This will be mentioned, and finally the use of the formulation in the emulsion polymerization of the latex will be mentioned.
    Fatty alcohol ethoxylates. Suitable fatty alcohol ethoxylates are compounds of the formula RO (CH 2 CH 2 O) n H, RO (EO) X , or RO-X-EO, wherein R is alcohol and n and X are 1 mole of alcohol The number of moles of sugar ethylene oxide units. Fatty alcohol residues can be developed from any animal, natural or synthetic source. However, it should be noted that the ethoxylation of fatty alcohols is much greater than that commonly encountered in detergent type fatty alcohol ethoxylates. In particular, the degree of ethoxylation is preferably 14 or more, even more preferably at least 20 to 50. Suitable fatty alcohol ethoxylates include tallow alcohol-40-ethoxylate, lauryl alcohol-30-ethoxylate, lauryl alcohol-20-ethoxylate, lauryl alcohol-50-ethoxylate, lauryl Alcohol-40-ethoxylate, tallow-20-ethoxylate, tallow-30-ethoxylate, C 12 -C 16 -31EO, lauryl-23EO, C 30 -40EO and C 50 -16EO . Suitable secondary alcohol ethoxylates include C 11 -C 15 -15 EO, C 11 -C 15 -20 EO, C 11 -C 15 -30 EO and C 11 -C 15 -40 EO. Suitable branched tridecyl alcohol ethoxylates are C 13-14 EO and C 13-15 EO. Further suitable alcohol ethoxylates are oleyl alcohols having 200 EO. The nonionic surfactants described above are representative examples and are not all examples. Those skilled in the art will appreciate that the molar ratio of ethoxylate to alcohol is an approximate ratio, not an absolute ratio.
    Alkylpolyglycosides. The object of the present invention exhibits the advantageous properties of alkyl glycosides on the one hand, that is, they can be prepared from natural raw materials which can be used and recovered in general, and on the other hand, nonionics known to date An emulsifier, for example an emulsifier for emulsion polymerization, is at least equivalent in terms of technical properties and addition products of alkyl phenols and ethylene oxide, which are now believed to be environmental hormones. Thus, the present invention relates to the use of alkyl glycosides and reducing sugars of C 8 -C 22 alkanols, wherein one sugar chain containing on average 1 to 10 sugar residues attached to each other by glycosidic bonds is ethylene It exists in any alkyl group as a common emulsifier at the time of emulsion polymerization of an unsaturated monomer.
    Alkylpolyglycosides used according to the invention can be prepared, for example, by the process according to US Pat. No. 3,839,318. In this method, for example, sugars such as glucose or oligosaccharides, and alcohols with the desired chain length, for example C 6 -C 18 , are reacted at 80 ° C. to 130 ° C. in the presence of an acid catalyst such as sulfuric acid. The water to be reacted is separated by vacuum distillation or azeotropic distillation, and any change in glucose is greatly avoided by monitoring the reaction temperature and catalyst concentration.
    Suitable polymerization emulsifiers are alkyl glycosides wherein the alkyl group is from C 8 -C 22 alcohols and the sugar residues are from reducing sugars. Alkyl groups may be straight or branched or may contain even or odd carbon atoms and, if desired, one or more olefinic double bonds.
    Alkyl polyglycosides that can be used in the present invention have the general formula (I):
    R 1 O (R 2 O) b (Z) a
    Where
    R 1 is a monovalent organic radical having about 6 to about 30 carbon atoms;
    R 2 is a divalent alkylene radical having 2 to 4 carbon atoms;
    Z is a saccharide residue having 5 or 5 carbon atoms;
    b is a number having a value from 0 to about 12;
    a is a number having a value from 1 to about 6. Preferred alkyl polyglycosides which can be used in the compositions according to the invention have the formula (I) wherein Z is a glucose moiety and b is zero. Such alkyl polyglycosides are commercially available, including, for example, APG (registered), Glucophone (GLUCOPON) available from Henkel Corporation, 19002 Pennsylvania, Amble; Registered), PLANTAREN (registered) or AGRIMUL (registered) surfactant. Examples of such surfactants include, but are not limited to, the surfactants described below:
    1. Glucophone (registered) 220 surfactant-alkyl polyglycosides having an alkyl group containing 8 to 10 carbon atoms and an average degree of polymerization of 1.5.
    2. Glucophone (registered) 225 surfactant-Alkyl polyglycosides having an alkyl group containing 8 to 10 carbon atoms and an average degree of polymerization of 1.7.
    3. Glucophone (registered) 600 surfactant-alkyl polyglycosides having an alkyl group of 12 to 16 carbon atoms and an average degree of polymerization of 1.4.
    4. Glucophone (registered) 625 surfactant-alkyl polyglycosides having an alkyl group of 12 to 16 carbon atoms and an average degree of polymerization of 1.4.
    5. APG® 325 surfactant-Alkyl polyglycosides having an alkyl group containing 9 to 11 carbon atoms and an average degree of polymerization of 1.6.
    6. Planarene (registered) 2000 surfactant-Alkyl polyglycosides having an alkyl group of 8 to 16 carbon atoms and an average degree of polymerization of 1.4.
    7. Planarene (registered) 1300 surfactant-Alkyl polyglycosides having an alkyl group of 12 to 16 carbon atoms and an average degree of polymerization of 1.6.
    8. Agrimal (registered) PG 2067 surfactant-Alkyl polyglycosides having an alkyl group containing 8 to 10 carbon atoms and an average degree of polymerization of 1.7.
    Other examples include U.S. Pat. There is an alkyl polyglycoside surfactant composition consisting of a mixture of compounds of formula (I) as described in patents 5,266,690 and 5,449,763.
    According to the invention, preference is given to using alkyl glycosides of the type derived from fatty alcohols. Preferred alkyl glycosides are alkyl glycosides of fatty alcohol mixtures having a chain length of C 8 , C 10 , C 12 , C 14 , C 16 or C 18 , wherein the C 16 or C 18 groups are from 1 to 3 ethylenically unsaturated Optionally contains a double bond.
    Where the saccharide portion of an alkyl glycoside is of interest, alkyl glycosides having sugar chains containing on average 1 to 10 sugar residues attached to each other by glycosidic bonds are suitable. Although sugar residues of different reducing sugars can be used, glucose and maltose are preferred. The number of sugar residues is the statistical mean on which the distribution representing these products is based. Particularly suitable emulsifiers are alkyl glycosides containing on average 1.4 to 5 sugar molecules and more particularly 1.4 to 5 glucose molecules per alkyl group. The average degree of glycoside polymerization of at least one alkylpolyglycoside is preferably from about 1.4 to about 1.8.
    Among these surfactants, alkyl glycosides having a C-chain length of C 8 -C 14 are particularly preferred. Such products can be prepared, for example, by reacting palm oil fatty alcohols with glucose according to Example 6 of US Pat. No. 3,839,318, described above. Preferred alkylpolyglycosides are Glucophone 220, Glucophone 225, Glucophone 425, Glucophone 600, and Glucophone 625, all of which are trademarks of Henkel Corporation, Ambler, Pennsylvania. Preferred alkylpolyglycosides, ie, the alkyl moieties of Glucophone 220, are mixtures having a carbon length of 8 to C 10 , on average 9 to 9.1 carbons, with an average degree of glycoside residue polymerization of 1.5. It is supplied as 60% solids in water. Glucophone 600 has an alkyl residue of C 12 to C 16 .
    As used herein, the term "APS" refers to "alkylpolysaccharides" such as alkylpolyglycosides, and "glucophone 220" is a 60% solution of a particular APS. However, to clarify the total amount of water in the composition, the artificial concept "APS 220" is used. "APS 220" is intended to represent a 100% active solids modification of Glucophone 220. In formulations where% solids appear to have a higher probability than is possible by using 60% solid APS, the formulation was concentrated by evaporating excess water and the formulation was made from 100% solid APS, "APS 220". Reported.
    APS / FAE / water combination. Preferred ranges of the components of the surfactant combination are 20% to 76% by weight fatty alcohol ethoxylate, 4% to 40% by weight alkylpolyglycoside and 20% to 60% by weight water, wherein the weight percent is fatty alcohol The sum of ethoxylates, alkylpolyglycosides and water, with the weight percent of the fatty alcohol ethoxylates, alkylpolyglycosides and water being adjusted to be 100% total for any composition, the composition being gel or solid at room temperature There is no liquid. These compositions are shown as region 1 of FIG. 1. Particularly preferred compositions comprise 39 to 67.5 weight percent fatty alcohol ethoxylates, 5 to 35 weight percent alkylpolyglycosides and 22 to 45 weight percent water. These compositions are shown in region 3 of FIG. 1. Most of these compositions also have desirable properties that remain gel free when diluted with water.
    Certain compositions belonging to these regions include 46% by weight of lauryl alcohol-30-ethoxylate, 19% by weight of alkylpolyglycosides having an alkyl group with an average length of 9 carbon chains and an average degree of glycoside residue polymerization of about 1.5. And 35% by weight of water. This composition is at point 5 in FIG. 1.
    46% by weight tallow alcohol-40-ethoxylate, 28% by weight alkylpolyglycoside having an alkyl group having an average length of carbon chain of 9 and an average glycoside residue polymerization degree of 1.5, and 26% by weight water. This composition is at point 6 in FIG. 1.
    46 weight percent tallow alcohol-40-ethoxylate, 28 weight percent alkylpolyglycoside having an alkyl group having an average length of carbon chain of 9 and a polymerization degree of glycosidic residue of 1.5, and 26 weight percent water. This composition is at point 8 in FIG. 1.
    46 wt% lauryl alcohol-20-ethoxylate, 19 wt% alkylpolyglycoside and 35 wt% water with an alkyl group having an average length of 9 carbon chains and an average glycoside residue polymerization degree of 1.5. This composition is at point 5 in FIG. 1.
    46% by weight of lauryl alcohol-50-ethoxylate, 19% by weight of alkylpolyglycoside and 35% by weight of water having an alkyl group having an average length of 9 in the carbon chain and having an average glycoside residue polymerization degree of 1.5. This composition is also at point 5 in FIG. 1.
    46 wt% lauryl alcohol-40-ethoxylate, 19 wt% alkylpolyglycoside and 35 wt% water with an alkyl group having an average length of 9 carbon chains and an average glycoside residue polymerization degree of 1.5. This composition is also at point 5 in FIG. 1.
    46% by weight of lauryl alcohol-30-ethoxylate, 10% by weight of alkylpolyglycoside and 35% by weight of water having an alkyl group having an average length of 9 in the carbon chain and having an average glycoside residue degree of polymerization of 1.5. This composition is at point 7 in FIG.
    50.2 wt% lauryl alcohol-20-ethoxylate, 16.8 wt% alkylpolyglycoside and 33 wt% water with an alkyl group having an average length of 9 carbon chains and an average glycoside residue polymerization degree of 1.5. This composition is at point 9 in FIG.
    50% by weight of lauryl alcohol-20-ethoxylate, 15% by weight of alkylpolyglycoside and 35% by weight of water having an alkyl group having an average length of 9 in the carbon chain and having an average glycoside residue degree of polymerization of 1.5. This composition is at point 11 in FIG. 1.
    48 wt% lauryl alcohol-40-ethoxylate, 16 wt% alkylpolyglycoside and 36 wt% water with an alkyl group having an average length of 9 carbon chains and an average glycoside residue polymerization degree of 1.5. This composition is at point 13 in FIG.
    55.5 wt% lauryl alcohol-50-ethoxylate, 18.5 wt% alkylpolyglycoside and 26 wt% water with an alkyl group having an average length of 9 carbon chains and an average glycoside residue polymerization degree of 1.5. This composition is at point 15 in FIG.
    50% by weight of lauryl alcohol-20-ethoxylate, 15% by weight of alkylpolyglycoside and 35% by weight of water having an alkyl group having an average length of 9 in the carbon chain and having an average glycoside residue degree of polymerization of 1.5. This composition is also at point 11 in FIG. 1.
    Preferred techniques for the preparation of these blends on a large scale to minimize intermediate gel formation generally include heating the water above the surfactant cloud point, which will approximate the boiling point or boiling point, adding the surfactant with stirring, and cooling with stirring. will be.
    Surfactant combinations (lauryl alcohol ethoxylates) of APS 220 and 600 with disfonyl LS20, LS30, LS40 and LS50 were prepared. Disconil TA 20, 30 and 430 and APG surfactant combinations (tallow alcohols 20, 30 and 40 ethoxylates respectively) were also prepared. Phase diagrams of these systems were determined. Vinyl acetate / butyl acrylate latex was prepared using Trycol 6970 (APE) and disfonyl 3065 and 4065 (APG surfactant 110 containing the blend) as well as these surfactants.
    Compared to the latex synthesized using Trycol 6970, it was found that the level of coagulant is reduced by the approximate size for the combination of LS 30 and TA430 with APG surfactant 220 and APG surfactant 600. The particle size distribution was comparable. APG surfactant 220 improved the phase behavior of disfonyl by increasing the temperature range in which the liquid formulation can be maintained. This has a very close relationship to product quality, ease of manufacture, storage and product transportability.
    Additional surfactants and other components can be incorporated into the APS / FAE blend or latex containing them. The APS / FAE / water combination of the present invention can be combined with anionic, cationic and other nonionic emulsifiers.
    Suitable anionic emulsifiers include sulfocarboxylic acids, alkyl esters thereof, fatty alcohol (ether) sulfates, alkyl phenol (ether) sulfates, sulfosuccinic acid (semi) esters and / or soaps of natural or synthetic origin. . Examples of other emulsifiers are unbalanced resin soaps, water-insoluble salts of branched monocarboxylic acids obtainable by the product of the reaction called Guerbet reactions, alkyl benzene sulfonates, paraffin sulfonates, alkyls Naphthalene sulfonates, water-insoluble salts of sulfate oils, alkyl ether phosphates, alkyl phenol ether phosphates, aminoalkanol sulfonic acids and / or alkyl diphenyl ether sulfonates.
    According to the invention, APS / FAE / water combinations can also be used in combination with cationic emulsifiers, for example with fatty amine hydrochloride or quaternary ammonium compounds. Other emulsifiers that may be combined with APS / FAE / water mixtures include additional nonionic emulsifiers, for example ethoxylates of fatty acids and fatty acid ester ethoxylates. In addition, APS / FAE / water combinations can also be used with ionic mixed compounds, ie long chain betaines or sulfobetaines. When the alkyl glycosides of the present invention are combined with other emulsifiers, it is advisable to use these other emulsifiers in amounts of 10 to 80% by weight, preferably in amounts of 20 to 50% by weight, based on the alkyl glycosides. desirable. One combination consists of sulfofatty acid esters, sulfofatty acids, and APS / FAE / water combinations used in accordance with the present invention.
    In order to solve certain problems associated with emulsion polymerization, it may be appropriate to use APS / FAE / water combinations with protective colloids. In this case, however, it is important to ensure that the emulsion polymerization actually takes place mechanically, ie the polymerization takes place in the micelles to ensure the production of latiss with a particle size smaller than the starting dispersion.
    Emulsion Polymerization of Latex. In a first embodiment of the invention, the APS / FAE / water combination can be used in emulsion polymerization of vinyl esters. Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl-2-hexyl hexanate and also esters of higher vinyl alcohols. The emulsifiers are also suitable for use in the polymerization of vinyl halides, preferably vinyl chloride or vinylidene chloride.
    In another embodiment of the invention, the APS / FAE / water mixture can be used in combination with an anionic emulsifier, preferably in the emulsion polymerization of olefins. Suitable olefins are, for example, styrene or other aromatic vinyl compounds, for example α-methyl styrene or isobutene. The emulsifiers can also be used in the emulsion polymerization of diolefins, for example, most broadly based on rubber latices, ie, butadiene, isoprene, chlorinated butadiene, chlorinated isoprene or styrene based latices and / or acrylonitrile It can be used to prepare a latiss based on a copolymer of and diolefin.
    In another embodiment of the invention, the APS / FAE / water mixture may be used with anionic emulsifiers, preferably in emulsion polymerization of esters and / or amides of acrylic acid and / or methacrylic acid. As such, the compounds may be used in the polymerization of methyl, ethyl, propyl, isopropyl, butyl, hexyl and / or 2-ethylhexyl esters of acrylic acid and / or methacrylic acid. Emulsifiers may also be used in the emulsion polymerization of N-alkylamides of acrylic acid and / or methacrylic acid.
    In another embodiment of the present invention, the APS / FAE / water blend can be used with anionic emulsifiers as desired in the emulsion polymerization of vinyl esters. Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl-2-hexyl hexanate and also esters of higher vinyl alcohols. The emulsifier can be used for the polymerization of vinyl halides, preferably vinyl chloride or vinylidene chloride.
    Emulsifier mixtures may also be used in the copolymerization of one or more of the aforementioned monomers, optionally with other partially water-insoluble monomers. As such, they are suitable for use in the copolymerization of acrylonitrile, methacrylonitrile, maleate or fumarate, for example di-n-butyl maleate or monobutyl maleate with ethylenically unsaturated monomers.
    Finally, the APS / FAE / water emulsifier mixture is also a mixture of different monomers, for example a mixture of styrene and acrylate, a mixture of vinyl acetate and ethylene or a mixture of vinyl acetate and vinyl chloride and a long chain vinyl ester and vinyl acetate Is suitable for use in the emulsion polymerization of mixtures of polyhydric acid vinyl esters. Water-insoluble monomers include vinyl acetate, butyl acrylate, styrene, butadiene, methyl methacrylate, methyl acrylate, chloroprene, vinyl chloride, acrylonitrile, acrylamide, ethylene, ethylene acrylate, vinyl versatate, maleic anhydride 2-ethyl hexyl acrylate and mixtures thereof are particularly preferred.
    Also within the scope of the present invention, emulsifiers are used for the copolymerization of separable water-insoluble monomers and ethylenically unsaturated water-insoluble monomers, wherein the separable water-insoluble monomers are 40% by weight based on the total monomers. Less than, preferably 0.5 to 15% by weight.
    Suitable water-insoluble separable monomers include semiesters of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic acid or fumaric acid, crotonic acid, vinyl sulfonic acid, vinyl phosphonic acid and / or 2-acrylicamino-2 Methylpropane sulfonic acid. The acid is preferably used in the form of a salt, for example an alkali metal salt or an ammonium salt. Other suitable comonomers are basic esters of acrylic acid and / or methacrylic acid, for example dimethylaminoethyl methacrylate.
    When APS / FAE / water combinations are used according to the invention, the preferred ratio of monomers to water is 1: 3 to 1: 1 by weight. Standard adjuvants may be used with the emulsifier in the emulsion polymerization process. Such auxiliaries are, for example, polymerization initiators and / or accelerators such as potassium or ammonium persulfate, hydrogen peroxide, reducing agents such as sulfite or dithionate, transition metal compounds and the like. Due to the comparatively low stability of alkyl glycosides above pH 7, it is preferred to use buffers such as sodium hydrogen carbonate or sodium pyrophosphate, acetate or sodium acetate as additional auxiliaries.
    It is also possible to use molecular weight modifiers such as mercaptoethanol, thioglycolic acid, or organic sulfur compounds comprising thioglycolic acid esters with polyhydric alcohols such as ethylene glycol or glycerol.
    In emulsifiers suitable for use according to the invention, the emulsion polymerization is carried out at ordinary temperatures, for example 0 to 120 ° C., preferably at 40 to 100 ° C. and elevated pressure in the case of normal pressure or gaseous monomers. It can be performed under. Various additional methods known to those skilled in the art of polymerization can be used. As such, the emulsion can be prepared in a reaction vessel and then polymerized or, if desired, monomers, adjuvants or even emulsions can be added continuously or batchwise during the reaction.
    As can be seen through the following examples, which are not presented to be limiting, low coagulation, stable dispersions are obtained by the APS / FAE / water blend.
    Example 1
    Vinyl acrylic latex was prepared using the following method.
    Vinyl Acrylic Latex Synthetic Method Formulation sheet of vinyl acetate / butyl acrylate latexPremixing of MonomersWeight (gm) matterTotal weight monomers (gms) =270 Monomer 1 (vinyl acetate) =229.5 Monomer 2 (butyl acrylate) =40.51st fillerwater249.3 Anionic (28% Avirol 2010 = (Registered; Henkel Products, Sodium Lauryl Sulfate)4.82 Nonionic (LS30 / APS @ 65% solid) = (LS30 = 30mol ethoxylate lauryl alcohol) 55% LS30 (6.23 × 0.55 = 3.45 g) 10% APS (6.23 × 0.10 = 0.63) 35% water (6.23 × 0.35 = 2.15 g)6.23 Sodium persulfate1.01 Sodium bicarbonate0.5 FeCl 3 (trace)0.01 PH control with 85 wt% phosphoric acid3.5 Spray to liquid with N 2 until T = 55 ℃Burner adjustmentStirred at 150 rpmRecord your departure time 2nd fillerT = 55 ℃10% monomer mixture addedUse eye drops dropperT <60 ℃ maintenanceMix for about 5 minutes Pumping scrubbing with isopropyl alcohol and then water 3rd fillerReducing agent manufacturingSFS (Sodium Formaldehyde Sulfoxylate)0.5 30% NH 4 OH0.5 water0.5 Add 1 ml using dropperAdded to reactor with dropwise additionSlowly add at 12 drops / minute using a funnelTime recording
    4th fillerPumping residual monomers@ 3 g at 1 g / minPump Gauges = 40Dropping SFS solutionAfter adding all monomersMix for 30 minutes 5th fillerTBHP (tributylhydroperoxide) solution preparation: For 70% liquid, dilute 1.4gm TBHP to 100gm Otherwise solid: THBP solidOne water10 Add new drops to the flaskTemperature monitorRun reaction for 15 minutes if T increasesRe-add and check TIf T is constant, start coolingUse until all monomers are consumed % solid49
    Physical and application properties were tested for vinyl acrylic latex containing LS30 and APS 220 at different weight percents and in a ratio of 3 to 1 for anionic surfactants. The LS30 / APS 220 mixture was then replaced with another surfactant. Latexes made with these surfactants were also tested. ABEX at 1.5% (registered; New Jersey Cranberry Row Fullenk, Rhone Poulenc, Inc .; believed to be a mixed ethoxylate of straight and branched chains), and 1.5% and APS 220 to LS 30 Compared to 3065 (registered; commercially available from Henkel as disfonyl A 3065, mixed donut alcohol ethoxylate) at different ratios, coagulum in the APS 220 / LS 30 mixture was significantly reduced. Latex containing APS 220 / LS30 at the same level as nonyl phenol ethoxylate showed an 83% increase in shear stability. Latexes containing the LS30 / APS 220 mixture at 1.5% concentration levels, such as ABEX, 3065 and Tricol 6970 (nonyl phenol ethoxylate), showed equivalent water absorption. However, there is an optimal level of LS30 / APS 220 that will provide minimal moisture absorption in this monomer system. Physical and application or film properties are summarized in Table 2 below.
    Physical and film properties Surfactant levelpH% solidParticle size (nm)% COAGPendulum hardnessShear stability (min)H 2 O Ads.MEK rub APS220 / LS301.54.247.68174.60.1753.000.330.002296.15 APS220 / LS302.04.247.82164.50.1950.000.250.000498.17 APS220 / LS303.04.947.321850.1060.331.000.004299.33 APS220 / LS304.05.048.49174.40.6846.330.330.003497.98 ABEX 25251.53.847.49172.90.2572.330.330.002099.90 Tricoll 69701.54.847.93156.90.4069.330.180.002999.89 Disfonyl 30651.54.748.10188.60.3474.330.180.001599.68
    Surfactant levels are in weight percent based on monomers (BOM).
    H 2 O Ads is the percent change in film weight following immersion in water.
    Example 2
    Vinyl acrylic and maleic acid. The same redox method as in Example 1 was used except that 85% by weight of vinyl acetate, 15% by weight of butyl acrylate and 0.2% by weight of maleic anhydride were used. In addition, the pH of the first charge was adjusted with acetic acid rather than with phosphoric acid. Nonionic surfactant levels were maintained in 1.5 wt% BOM and anionic surfactant levels were maintained in 0.5 wt% BOM. Tests were also made at varying ratios of LS30 to APS 220. The reduction of coagulum due to the use of APS 220 / LS30 at a weight ratio of 10/55 was found to be associated with other surfactants. Nonionic formulations containing 55% LS30 and 10% APS 220 are preferred compositions.
    The mechanical stability provided to the latex by the APS 220 / LS30 surfactant system was better than the other surfactants tested. A decrease in water absorption of the latex containing the APS 220 / LS30 surfactant mixture to the dry film was observed to be related to the other surfactants tested. The minimum film formation temperature (MFT) of maleic anhydride containing vinyl acrylic latex made from APS 220 / LS30 was 16 ° C. The MFT of ABEX containing the material was 29 ° C. ABEX containing latex could not form a film at room temperature (25 ° C). APS 220 / LS30 containing latex films showed better solvent resistance. A summary of the physical and film properties of maleic anhydride containing vinyl acrylic latex is shown in Table 3 below.
    Physical and Film Properties of Vinyl Acrylics Containing Maleic Anhydride SurfactantsParticle size (nm)pHWt% solids% By weight coagulantPendulum hardnessMechanical stabilityH 2 O AdsMEK APS220377.53.918.4281.5712.00TMC081.14 30/35 LS30 / APS220330.84.131.6872.60NFFTMCNFFNFF 42.5 / 22.5 LS30 / APS220220.13.822.0549.206.67TMC0.000188.73 55/10 LS30 / APS220231.34.049.790.1831.671.60.000143.75 Tricoll155.73.950.040.3142.330.50.000363.87 ABEX212.63.850.360.44NFF0.5NFFNFF
    TMC = (Too Much Coagulum; Excess Coagulum), NFF = (No Film Formed; No Film Formed)
    Example 3
    100% acrylic latex was prepared using the method of Table 4.
    100% acrylic latex way Formulation for 100% acrylic latex Filling in reactor 1 ingredientactivation%Working weight (g)Active solids (g)% Based on 100 parts monomer DI water 180 LS30 / APS220650.520.340.075 Heating the filling to a temperature of 1 to 80 ° C Clean with N 2Maintained at N 2 throughout all 180.520.34Monomer Premix DI water 210 Anionic: Avirol 2010 (28%)288.042.250.5 LS30 / APS220 @ 65% Solids6517.3111.252.5 Methyl methacrylate10022022048.03 Butyl acrylate10022022048.03 Styrene100 0.00 Methylacrylic acid1004.54.50.98 all 679.84458Initiator premix DI water 55.4 Ammonium persulfate 2.252.250.5 all 57.652.25Filling 2 Add 25% initiator solution (11.25 g) at 80 ° C Add 5% (35.7 g) of monomer solution Hold at 80 ° C. for 15 minutes Filling 3 Residual monomer feed (3.8 g / min) over 3 hours About 6 drops / min of residual initiator feed (0.258 g / min) over the same 3 hoursAfter 3 hours, heat the reactor to 85 ° C. for 30 minutes Cool to room temperature % Solids = 50.17 Adjust pH to 7 if desired
    In a 100% acrylic system, the surfactant was used at the same concentration level (2.5% nonionic based on monomer) and the coagulation level of the latex containing the LS30 / APS 220 blend was the lowest. The particle size of the LS30 (55%) / APS 220 (10%) surfactant-containing latex was statistically equivalent to the particle size of the latex made of Tricol (NPE). Latex films containing LS30 / APS 220 showed lower moisture absorption. The properties are listed in Table 5 below.
    Physical and Film Properties of 100% Acrylic Latex SurfactantsParticle size (nm)pHWt% solids% By weight coagulantPendulum hardnessMesh stability (seconds)H 2 O Ads (%)MEK Rub (%) Tricoll1641.8501.428150.05293.7 45/20 LS30 / APS2201872500.528144089.2 55/10 LS30 / APS2201692.3500.8828100.001898.9 ABEX 25251802.250230300.001193.46
    Example 4
    The styrene acrylic latex method is shown in Table 6 below.
    Styrene acrylic latex method Filling in reactor 1 ingredientactivation%Working weight (g)Active solids used (g)% Based on 100 parts monomer DI water 180 LS30 / APS220650.520.340.075 Heating the filling to a temperature of 1 to 80 ° C Clean with N 2Keep N 2 Throughout all 180.520.34Monomer Premix DI water 210 Anionic Avirol 2010 (28%)288.0362.250.5 LS30 / APS220 @ 65%6517.3111.252.5 Methyl methacrylate10025255.35 Butyl acrylate10021221245.40 Styrene10021221245.40 Methacrylic acid1004.54.50.96 all 688.84467Initiator premix DI water 55.4 Ammonium persulfate 2.252.250.5 all 57.652.25Filling 2 Add 25% initiator solution (11.25 g) at 80 ° C Add 5% (35.7 g) of monomer solution Hold at 80 ° C. for 15 minutes Filling 3 Residual monomer feed (3.8 g / min) over 3 hours Approximately 6 drops / minute of residual initiator feed (0.258 g / minute) over 3 hoursAfter 3 hours, heat the reactor to 85 ° C. for 30 minutes Cool to room temperature % solid 50.6 Adjust pH to 7 if desired
    The coagulum for the LS30 / APS 220 surfactant blend was much lower than the nonylphenol ethoxylates used at 2.5% based on monomers present as 0.5% anions. The particle size of the latex containing the LS30 / APS 220 blend was equal to or slightly smaller than the particle size of nonyl phenol ethoxylate (2.5% based on monomers where 0.5% is an anion) at the same weight percent. Water absorption of the styrene acrylic film was reduced to some extent by replacing nonyl phenolic surfactant (Tricol 6970) with the LS30 / APS 220 blend at the same activity level. Film properties are listed in Table 7 below.
    Styrene Acrylic Latex Film Properties Surfactants% By weight coagulantWater Ad%Pendulum hardnessMesh stabilityMEK Rub Tricoll 69700.50.06431.8398.4 LS30 (45) APS220 (20)0.470.04482.7598.5 LS30 (55) APS220 (10)0.330.002422.599.7 Disfonyl 30650.250.001441.598.4
    Example 5
    Binary phase diagram for LS 30-APS 220-water surfactant system:
    The liquid phase region is defined in the phase diagram below. The total solids level of the blend was brought to 65% and subsequently diluted to give a composition with low solids content. To prepare a blend with at least 65% total solids, the 65% solid blend was placed in an oven and water was evaporated to achieve the desired composition with a high solids content. The first phase diagram shows a diagram of LS 300,000 as a control in FIG. 2 and shows phases of liquid 19, liquid + gel 21, liquid + solid 23, gel 25 and solid 27 It was. LS 30 is a 100% active linear ethoxylated alcohol. Phase diagram of LS 30 (60%) / APS220 (5%) / water (35%) formulation shows liquid 29, liquid + solids (31, 33), gel 35 and solid (37) phases 3 is shown. While not wishing to be bound by any theory, it is believed that an increase in the amount of APS 220 surfactant gradually liquefies the LS 30 / APS 220. This is shown in Figures 4-8.
    4 shows a binary phase diagram of disponyl LS30 (lauryl alcohol 30-ethoxylate), 55:10 (wt% active) APS 220, varying the amount of water (100%-% solids). The liquid 39, liquid + gel 41, gel 43 and solid 45 phases are shown.
    FIG. 5 shows a binary phase diagram of disponyl LS30 (lauryl alcohol 30-ethoxylate), 50:15 (wt% active material) APS 220 while varying the amount of water (100%-% solids). The liquid 47, liquid + solid 49, gel 51 and solid 53 phases are shown. It should be noted that a mixture of about 60% solids can be infinitely diluted at 20 ° C. without going through the gel phase which particularly facilitates dispersion.
    FIG. 6 shows a binary phase diagram of disponyl LS30 (lauryl alcohol 30-ethoxylate), 43:22 (wt% active) APS 220, varying the amount of water (100%-% solids). The liquid 55, liquid + solid 57 and solid 59 phases are shown. It does not have any undesirable gel phase at temperatures above the freezing point.
    FIG. 7 shows a binary phase diagram of disponyl LS30 (lauryl alcohol 30-ethoxylate), 35:30 (wt% active) APS 220, varying the amount of water (100%-% solids). The liquid 61, liquid plus solids 63 and 65 and solid 67 phases are shown. It does not have any undesirable gel phase at temperatures above the freezing point.
    FIG. 8 shows the binary phase diagram of APS 220 and water (control), showing the liquid 69, liquid + gel 71 and solid 73 phases.
    Example 7
    Dual phase diagram of LS 50 (50 mol ethoxylate lauryl alcohol) / APS surfactant 220 / water system: The phase diagram of the LS50 is shown in FIG. 9 as a control, where FIG. 9 shows liquid 75 , Liquid + gel 85, gel 83, gel + solid 81, liquid + solid 77, and solid 79 phases. This is mostly solid 79 except in the case of very high or very low solids content. This makes the material unacceptable as a surfactant for emulsion polymerization. The addition of a small amount of APS 220 surfactant (10% by weight) added LS50 / APS 220 surfactant to 60% solids content as shown in FIG. 10 showing the liquid + solids (89, 91) and solid (93) phases. Liquefy. Increasing the APS 220 level in the mixture above 10% does not significantly increase the flow zone 95. This is shown in FIG. 11, which also shows the liquid + solid 97 and solid 99 phases. At 30% APS 220, the flow zone 101 is slightly increased from 60% total solids to 65% total solids, as shown in FIG. 12 which also shows the liquid + solid 103 and solid 105 phases.
    A mixture of tallow alcohol 40-ethoxylate was prepared from APS 220: FIG. 13 shows TA 430 (registered; Henkel Corporation, tallow alcohol 40-ethoxylate) with varying water (100%-% solids), The binary phase diagram of the 50:30 (wt% active material) APS 220 is shown, showing the liquid 107, liquid plus solid 109 and solid 111 phases.
    FIG. 14 shows the binary phase diagram of TA 430 (registered; Henkel Corporation, Tallow Alcohol 40-Ethoxylate), 40:36 (wt% active material) APS 220 with varying water (100%-% solids). And liquid phase 113, liquid plus solid 115 and solid 117 phases.
    Example 8
    Vinyl Acrylic Latex Prepared from LS50 / APS 220 Surfactant Formulation: The vinyl acrylic latex method described in Example 1 was performed. LS30 / APS 220 surfactant formulation was replaced with LS50 / APS 220 surfactant. Vinyl acrylic latex was prepared using Tricol 6970 (nonyl phenol 40 mol ethoxylate) surfactant. The water absorption of the LS50 / APS 220 surfactants containing latex was found to be much lower than Tricol 6970. The LS50 / APS 220 surfactant formulation containing latex showed significantly lower coagulum compared to the latex formulated with Tricol 6970. The mechanical stability of the LS50 / APS 220 surfactant containing latex was much greater than the latex made with Tricol 6970. The results are shown in Tables 8 and 9 below.
    Physical Properties of Vinyl Acrylic Latex LS50 pH% solidParticle size% CoagulumHardness 5510 4.747.81165 0.15 64.67 4520 4.847.65164.8 0.43 66.67 3530 5.047.24178.4 0.11 69.33 Tricoll 69704.847.49156.9 0.40 69.33 Disfonyl 30654.749.69188.6 0.34 74.33
    5510, 4520 and 3550 represent the solid compounding ratio 55/10, 45/20, 35/30 of LS50 / APS 220 surfactant, respectively.
    Physical and Film Properties of Vinyl Acrylic Latex LS50 Water absorptionMechanical stabilityMEK loss rate 5510 0.0008 0.33 98.21 4520 0.0009 0.25 98.98 3530 0.0007 0.17 98.52 Tricoll 69700.0029 0.17 99.89 Disfonyl 30650.0015 0.17 99.68
    Example 10
    Vinyl acrylic latex made with TA30 / APS 220 surfactant blend and TA430 / APS 220 surfactant blend: generally, TA430 / APS 220 surfactant blend, TA30 / APS 220 surfactant blend, TA430 / APS 600 surfactant blend and TA30 Latexes made with the / APS 600 surfactant blend showed lower coagulants than latexes made with TA430 or TA30 alone or made with Tricol 6970 as shown in Example 1.
    Physical Properties of Vinyl Acrylic Latex Anionic surfactantNonionic surfactant% solidParticle sizeCoagulum (g)COAG% BOMpH Avivir 2010 (0.5%)Tricall (1%)45.20%178.41.40.525.7 Avirol 2010 (0.5%)Disfonyl 4065 (1%)43.60%196.5One0.375.6 Avirol 2010 (0.5%)Disfonyl 3065 (1%)43.60%210.90.90.335.2 Avirol 2010 (0.5%)APS 220UP (1%)45.00%184.80.60.224.8 Avirol 2010 (0.5%)APS 600UP (1%)44.10%218.60.730.276.6 Avirol 2010 (0.5%)Disfonyl LS 30 + APS 220 (1%)42.00%201.80.60.226.1 Avirol 2010 (0.5%)Disfonyl LS 30 (1%)44.40%257.30.80.306 Avirol 2010 (0.5%)Disfonyl TA 430 + APS 220 (1%)48.00%181.80.50.193.3 Avirol 2010 (0.5%)Disfonyl TA 430 + APS 600 (1%)47.80%251.31.30.482.6 Avirol 2010 (0.5%)Disfonyl TA 430 (1%)48.10%190.35.62.073.6 Avirol 2010 (0.5%)Disfonyl TA 30 + APS 220 (1%)48.50%210.40.80.303.1 Avirol 2010 (0.5%)Disfonyl TA 30 + APS 600 (1%)48.30%206.81.10.412.7 Avirol 2010 (0.5%)Disfonyl TA 30 (1%)48.00%258.71.20.443 Avirol 2010 (0.5%)Disfonyl TA 10 + APS 220 (1%)48.80%1750.640.244.5 Avirol 2010 (0.5%)Disfonyl TA 10 (1%)47.50%1777.92.935.9
    Note) "UP" represents the non-conserved form of each commercial APS.
    权利要求:
    Claims (113)
    [1" claim-type="Currently amended] From about 20% to about 76% by weight fatty alcohol ethoxylate with an ethoxylation degree of 14 or greater based on the total weight of fatty alcohol ethoxylate, alkylpolyglycoside and water; About 4% to about 40% alkylpolyglycoside; And about 20 wt% to about 60 wt% water, wherein the surfactant composition is a liquid free of gels or solid phase at room temperature.
    [2" claim-type="Currently amended] The composition of claim 1, wherein the composition remains in a liquid state upon dilution with water at about room temperature.
    [3" claim-type="Currently amended] The method of claim 1, wherein the alcoholic ethoxylate has a degree of ethoxylation of at least 14 from about 39 to about 67.5 weight percent; About 5 to about 35 weight percent alkylpolyglycoside; And from about 22% to about 45% by weight of water.
    [4" claim-type="Currently amended] The composition of claim 1, wherein the degree of ethoxylation is from about 20 to about 50.
    [5" claim-type="Currently amended] The composition of claim 1, wherein the ethoxylated fatty alcohol is substantially tallow alcohol-40-ethoxylate.
    [6" claim-type="Currently amended] The composition of claim 1 wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-30-ethoxylate.
    [7" claim-type="Currently amended] The composition of claim 1, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-20-ethoxylate.
    [8" claim-type="Currently amended] The composition of claim 1, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-50-ethoxylate.
    [9" claim-type="Currently amended] The composition of claim 1, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-40-ethoxylate.
    [10" claim-type="Currently amended] The composition of claim 1, wherein the ethoxylated fatty alcohol is substantially tallow-20-ethoxylate.
    [11" claim-type="Currently amended] The composition of claim 1 wherein the ethoxylated fatty alcohol is substantially tallow-30-ethoxylate.
    [12" claim-type="Currently amended] The composition of claim 1 wherein the alkyl group in the alkylpolyglycoside has from about 6 to about 10 carbon atoms.
    [13" claim-type="Currently amended] The composition of claim 1 wherein the alkyl group in the alkylpolyglycoside has from about 12 to about 16 carbon atoms.
    [14" claim-type="Currently amended] The composition of claim 1, wherein the average glycoside residue polymerization degree in the alkylpolyglycoside is about 1.5.
    [15" claim-type="Currently amended] The composition of claim 1 wherein the average glycoside residue polymerization degree in the alkylpolyglycoside is from about 1.4 to about 1.8.
    [16" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-30-ethoxylate is about 46% by weight; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [17" claim-type="Currently amended] 2. The composition of claim 1, wherein about 46% by weight of tallow alcohol-40-ethoxylate; About 28% by weight alkylpolyglycoside having an alkyl group of about 9 carbon atoms in average length having an average glycoside residue degree of polymerization of about 1.5; And about 26% by weight of water.
    [18" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-20-ethoxylate is about 46% by weight; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [19" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-50-ethoxylate is about 46% by weight; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [20" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-40-ethoxylate is about 46% by weight; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [21" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-30-ethoxylate is about 55% by weight; About 10% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [22" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-20-ethoxylate is about 50.2% by weight; About 16.8% by weight of an alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue polymerization degree of about 1.5; And about 33% by weight of water.
    [23" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-20-ethoxylate is about 50% by weight; About 15% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [24" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-40-ethoxylate is about 48% by weight; About 16% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and having an average glycoside residue degree of polymerization of about 1.5; And about 36% by weight of water.
    [25" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-50-ethoxylate is about 55.5% by weight; About 18.5% by weight of an alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 26% by weight of water.
    [26" claim-type="Currently amended] The method of claim 1, wherein the lauryl alcohol-30-ethoxylate is about 50% by weight; About 15% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [27" claim-type="Currently amended] The method of claim 1, wherein about 38% by weight of tallow alcohol-40-ethoxylate; About 34% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 28% by weight of water.
    [28" claim-type="Currently amended] (a) about 20% to 76% by weight fatty alcohol ethoxylate having an ethoxylation degree of 14 or greater based on the total weight of fatty alcohol ethoxylate, alkylpolyglycoside and water; About 4% to about 40% alkylpolyglycoside; And from about 20% to about 60% by weight of water;
    (b) water;
    (c) an effective amount of initiator; And
    (d) A stable latex composition comprising a product incorporating at least one substantially water-insoluble monomer.
    [29" claim-type="Currently amended] 29. The method of claim 28, wherein the surfactant composition comprises about 39 to about 67.5 weight percent fatty alcohol ethoxylate having an ethoxylation degree of 14 or greater; About 5 to about 35 weight percent alkylpolyglycoside; And from about 22% to about 45% by weight of water.
    [30" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the degree of ethoxylation is from about 20 to about 50.
    [31" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the ethoxylated fatty alcohol is substantially tallow alcohol-40-ethoxylate.
    [32" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-30-ethoxylate.
    [33" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-20-ethoxylate.
    [34" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-50-ethoxylate.
    [35" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-40-ethoxylate.
    [36" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the ethoxylated fatty alcohol is substantially tallow-20-ethoxylate.
    [37" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the ethoxylated fatty alcohol is substantially tallow-30-ethoxylate.
    [38" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the alkyl group in the alkylpolyglycoside has about 8 to about 18 carbon atoms.
    [39" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the alkyl group in the alkylpolyglycoside has about 12 to about 16 carbon atoms.
    [40" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the average glycoside residue polymerization degree in the alkylpolyglycoside is about 1.5.
    [41" claim-type="Currently amended] 29. The latex composition of claim 28, wherein the average glycoside residue degree of polymerization in the alkylpolyglycoside is from about 1.4 to about 1.8.
    [42" claim-type="Currently amended] 29. The composition of claim 28, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-30-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [43" claim-type="Currently amended] 29. The composition of claim 28, wherein the surfactant composition comprises about 46% by weight of tallow alcohol-40-ethoxylate; About 28% by weight alkylpolyglycoside having an alkyl group of about 9 carbon atoms in average length having an average glycoside residue degree of polymerization of about 1.5; And about 26% by weight of water.
    [44" claim-type="Currently amended] The method of claim 28, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-20-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [45" claim-type="Currently amended] 29. The composition of claim 28, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-50-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [46" claim-type="Currently amended] 29. The composition of claim 28, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-40-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [47" claim-type="Currently amended] The method of claim 28, wherein the surfactant composition comprises about 55% by weight of lauryl alcohol-30-ethoxylate; About 10% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [48" claim-type="Currently amended] The method of claim 28, wherein the surfactant composition comprises about 50.2% by weight of lauryl alcohol-20-ethoxylate; About 16.8% by weight of an alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue polymerization degree of about 1.5; And about 33% by weight of water.
    [49" claim-type="Currently amended] The method of claim 28, wherein the surfactant composition comprises about 50% by weight of lauryl alcohol-20-ethoxylate; About 15% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [50" claim-type="Currently amended] 29. The composition of claim 28, wherein the surfactant composition comprises about 48% by weight of lauryl alcohol-40-ethoxylate; About 16% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and having an average glycoside residue degree of polymerization of about 1.5; And about 36% by weight of water.
    [51" claim-type="Currently amended] The method of claim 28, wherein the surfactant composition comprises about 55.5% by weight of lauryl alcohol-50-ethoxylate; About 18.5% by weight of an alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 26% by weight of water.
    [52" claim-type="Currently amended] 29. The composition of claim 28, wherein the surfactant composition comprises about 38% by weight of tallow alcohol-40-ethoxylate; About 34% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 28% by weight of water.
    [53" claim-type="Currently amended] The method of claim 28, wherein the water-insoluble monomer is selected from vinyl acetate, butyl acrylate, styrene, butadiene, methylmethacrylate, methylacrylate, chloroprene, vinyl chloride, acrylonitrile, ethylene, vinyl versatate, ethyl acrylate, A latex composition, characterized in that it is selected from the group consisting of maleic anhydride, 2-ethyl hexyl acrylate and mixtures thereof.
    [54" claim-type="Currently amended] The method of claim 28, wherein the surfactant composition comprises about 50% by weight of lauryl alcohol-30-ethoxylate; About 15% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [55" claim-type="Currently amended] (a) from about 20% to about 76% by weight fatty alcohol ethoxylate with an ethoxylation degree of 14 or greater based on the total weight of fatty alcohol ethoxylate, alkylpolyglycoside and water; About 4% to about 40% alkylpolyglycoside; And from about 20% to about 60% by weight of water;
    (b) water;
    (c) an effective amount of initiator; And
    (d) contacting at least one substantially water-insoluble monomer to produce a latex.
    [56" claim-type="Currently amended] 56. The method of claim 55, wherein the surfactant composition comprises about 39 to about 67.5 weight percent fatty alcohol ethoxylate having an ethoxylation degree of 14 or greater; About 5 to about 35 weight percent alkylpolyglycoside; And from about 22% to about 45% by weight of water.
    [57" claim-type="Currently amended] 56. The method of claim 55, wherein the degree of ethoxylation is from about 20 to about 50.
    [58" claim-type="Currently amended] 56. The method of claim 55, wherein the ethoxylated fatty alcohol is substantially tallow alcohol-40-ethoxylate.
    [59" claim-type="Currently amended] 56. The method of claim 55, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-30-ethoxylate.
    [60" claim-type="Currently amended] 56. The method of claim 55, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-20-ethoxylate.
    [61" claim-type="Currently amended] 56. The method of claim 55, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-50-ethoxylate.
    [62" claim-type="Currently amended] 56. The method of claim 55, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-40-ethoxylate.
    [63" claim-type="Currently amended] 56. The method of claim 55, wherein the ethoxylated fatty alcohol is substantially tallow-20-ethoxylate.
    [64" claim-type="Currently amended] 56. The method of claim 55, wherein the ethoxylated fatty alcohol is substantially tallow-30-ethoxylate.
    [65" claim-type="Currently amended] 56. The method of claim 55, wherein the alkyl group in the alkylpolyglycoside has about 8 to about 10 carbon atoms.
    [66" claim-type="Currently amended] 56. The method of claim 55, wherein the alkyl group in the alkylpolyglycoside has about 12 to about 16 carbon atoms.
    [67" claim-type="Currently amended] 56. The method of claim 55, wherein the average glycoside residue polymerization degree in the alkylpolyglycoside is about 1.5.
    [68" claim-type="Currently amended] 56. The method of claim 55, wherein the average glycoside residue degree of polymerization in the at least one alkylpolyglycoside is from about 1.4 to about 1.8.
    [69" claim-type="Currently amended] 56. The composition of claim 55, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-30-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [70" claim-type="Currently amended] 56. The composition of claim 55, wherein the surfactant composition comprises about 46% by weight of tallow alcohol-40-ethoxylate; About 28% by weight alkylpolyglycoside having an alkyl group of about 9 carbon atoms in average length having an average glycoside residue degree of polymerization of about 1.5; And about 26% by weight of water.
    [71" claim-type="Currently amended] 56. The composition of claim 55, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-20-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [72" claim-type="Currently amended] The method of claim 55, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-50-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [73" claim-type="Currently amended] 56. The composition of claim 55, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-40-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [74" claim-type="Currently amended] The composition of claim 55, wherein the surfactant composition comprises about 55% by weight of lauryl alcohol-30-ethoxylate; About 10% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [75" claim-type="Currently amended] The composition of claim 55, wherein the surfactant composition comprises about 50.2% by weight of lauryl alcohol-20-ethoxylate; About 16.8% by weight of an alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue polymerization degree of about 1.5; And about 33% by weight of water.
    [76" claim-type="Currently amended] The composition of claim 55, wherein the surfactant composition comprises about 50% by weight of lauryl alcohol-20-ethoxylate; About 15% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [77" claim-type="Currently amended] 56. The composition of claim 55, wherein the surfactant composition comprises about 48% by weight of lauryl alcohol-40-ethoxylate; About 16% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and having an average glycoside residue degree of polymerization of about 1.5; And about 36% by weight of water.
    [78" claim-type="Currently amended] 56. The composition of claim 55, wherein the surfactant composition comprises about 55.5 weight percent of lauryl alcohol-50-ethoxylate; About 18.5% by weight of an alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 26% by weight of water.
    [79" claim-type="Currently amended] The composition of claim 55, wherein the surfactant composition comprises about 50% by weight of lauryl alcohol-30-ethoxylate; About 15% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [80" claim-type="Currently amended] The composition of claim 55, wherein the surfactant composition comprises about 38% by weight of tallow alcohol-40-ethoxylate; About 34% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 28% by weight of water.
    [81" claim-type="Currently amended] 56. The method of claim 55, wherein the water-insoluble monomer is vinyl acetate, butyl acrylate, styrene, butadiene, methyl methacrylate, methyl acrylate, chloroprene, vinyl chloride, acrylonitrile, acrylamide, ethylene, ethyl acrylate, vinyl Process selected from the group consisting of versatate, maleic anhydride, 2-ethyl hexyl acrylate, and mixtures thereof.
    [82" claim-type="Currently amended] A latex made by the method of claim 55.
    [83" claim-type="Currently amended] (a) from about 20% to about 76% by weight fatty alcohol ethoxylate with an ethoxylation degree of 14 or greater based on the total weight of fatty alcohol ethoxylate, alkylpolyglycoside and water; About 4% to about 40% alkylpolyglycoside; And from about 20% to about 60% by weight of water;
    (b) water;
    (c) an effective amount of initiator; And
    (d) contacting at least one substantially water-insoluble monomer to produce a latex, thereby reducing coagulum during emulsion polymerization.
    [84" claim-type="Currently amended] 84. The method of claim 83, wherein the surfactant composition comprises about 39 to about 67.5 weight percent fatty alcohol ethoxylate having an ethoxylation degree of 14 or greater; About 5 to about 35 weight percent alkylpolyglycoside; And from about 22% to about 45% by weight of water.
    [85" claim-type="Currently amended] 84. The method of claim 83, wherein the degree of ethoxylation is from about 20 to about 50.
    [86" claim-type="Currently amended] 84. The method of claim 83, wherein the ethoxylated fatty alcohol is substantially tallow alcohol-40-ethoxylate.
    [87" claim-type="Currently amended] 84. The method of claim 83, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-30-ethoxylate.
    [88" claim-type="Currently amended] 84. The method of claim 83, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-20-ethoxylate.
    [89" claim-type="Currently amended] 84. The method of claim 83, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-50-ethoxylate.
    [90" claim-type="Currently amended] 84. The method of claim 83, wherein the ethoxylated fatty alcohol is substantially lauryl alcohol-40-ethoxylate.
    [91" claim-type="Currently amended] 84. The method of claim 83, wherein the ethoxylated fatty alcohol is substantially tallow-20-ethoxylate.
    [92" claim-type="Currently amended] 84. The method of claim 83, wherein the ethoxylated fatty alcohol is substantially tallow-30-ethoxylate.
    [93" claim-type="Currently amended] 84. The method of claim 83, wherein the alkyl group in the alkylpolyglycoside has about 8 to about 10 carbon atoms.
    [94" claim-type="Currently amended] 84. The method of claim 83, wherein the alkyl group in the alkylpolyglycoside has about 12 to about 16 carbon atoms.
    [95" claim-type="Currently amended] 84. The method of claim 83, wherein the average glycoside residue degree of polymerization in the alkylpolyglycoside is about 1.5.
    [96" claim-type="Currently amended] 84. The method of claim 83, wherein the average glycoside residue degree of polymerization in the at least one alkylpolyglycoside is from about 1.4 to about 1.8.
    [97" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-30-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [98" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 46% by weight of tallow alcohol-40-ethoxylate; About 28% by weight alkylpolyglycoside having an alkyl group of about 9 carbon atoms in average length having an average glycoside residue degree of polymerization of about 1.5; And about 26% by weight of water.
    [99" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-20-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [100" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-50-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [101" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 46% by weight of lauryl alcohol-40-ethoxylate; About 19% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [102" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 55% by weight of lauryl alcohol-30-ethoxylate; About 10% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [103" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 50.2 weight percent of lauryl alcohol-20-ethoxylate; About 16.8% by weight of an alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue polymerization degree of about 1.5; And about 33% by weight of water.
    [104" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 50% by weight of lauryl alcohol-20-ethoxylate; About 15% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [105" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 48% by weight of lauryl alcohol-40-ethoxylate; About 16% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and having an average glycoside residue degree of polymerization of about 1.5; And about 36% by weight of water.
    [106" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 55.5% by weight of lauryl alcohol-50-ethoxylate; About 18.5% by weight of an alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 26% by weight of water.
    [107" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 50% by weight of lauryl alcohol-30-ethoxylate; About 15% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 35% by weight of water.
    [108" claim-type="Currently amended] 84. The composition of claim 83, wherein the surfactant composition comprises about 38% by weight of tallow alcohol-40-ethoxylate; About 34% by weight alkylpolyglycoside having an alkyl group having an average length of the carbon chain of about 9 and an average glycoside residue degree of polymerization of about 1.5; And about 28% by weight of water.
    [109" claim-type="Currently amended] 84. The method of claim 83, wherein the water-insoluble monomer is vinyl acetate, butyl acrylate, styrene, butadiene, methyl methacrylate, methyl acrylate, chloroprene, vinyl chloride, acrylonitrile, acrylamide, ethylene, ethyl acrylate, vinyl Process selected from the group consisting of versatate, maleic anhydride, 2-ethyl hexyl acrylate, and mixtures thereof.
    [110" claim-type="Currently amended] A latex made by the method of claim 83.
    [111" claim-type="Currently amended] 84. A latex made by the method of claim 83 containing less than about 1 weight percent coagulant based on monomer.
    [112" claim-type="Currently amended] The latex prepared by the method of claim 83, wherein the latex is all acrylic or styrene acrylic latex and contains less than about 3% by weight of alkylpolyglycoside and fatty alcohol ethoxylate based on monomers.
    [113" claim-type="Currently amended] 84. The latex produced by the method of claim 83, wherein the latex is a vinyl acrylic latex and contains less than about 1.5 weight percent alkylpolyglycoside and fatty alcohol ethoxylate based on monomers.
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    同族专利:
    公开号 | 公开日
    JP2002513432A|2002-05-08|
    EP1003606A2|2000-05-31|
    US6117934A|2000-09-12|
    AU731657B2|2001-04-05|
    BR9807304A|2002-06-04|
    EP1003606A4|2000-09-13|
    WO1998033876A2|1998-08-06|
    AU6243698A|1998-08-25|
    WO1998033876A3|2000-03-23|
    CA2278506A1|1998-08-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-02-03|Priority to US3704697P
    1997-02-03|Priority to US60/037,046
    1997-06-27|Priority to US5114597P
    1997-06-27|Priority to US60/051,145
    1997-12-15|Priority to US60/069,803
    1997-12-15|Priority to US6980397P
    1998-01-20|Priority to US9/009,432
    1998-01-20|Priority to US09/009,432
    1998-02-02|Application filed by 웨인 씨. 제쉬크, 헨켈 코포레이션
    2000-11-25|Publication of KR20000070738A
    优先权:
    申请号 | 申请日 | 专利标题
    US3704697P| true| 1997-02-03|1997-02-03|
    US60/037,046|1997-02-03|
    US5114597P| true| 1997-06-27|1997-06-27|
    US60/051,145|1997-06-27|
    US6980397P| true| 1997-12-15|1997-12-15|
    US60/069,803|1997-12-15|
    US9/009,432|1998-01-20|
    US09/009,432|US6117934A|1997-02-03|1998-01-20|Alkylpolyglycoside containing surfactant blends for emulsion polymerization|
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