CN1206013A - Aqueous copolymer dispersions of water-soluble monomers with N-vinyl groups and hydrophobic monomers - Google Patents

Abstract

An aqueous copolymer dispersion prepared by free-radical emulsion co-polymerization of a monomer mixture comprises (i) 10-70 wt% at least one nonionic monomer (A) containing a vinyl group and with a water- solubility, (ii) 30-90 wt% at least one monounsaturated, hydrophobic monomer (B) with a water-solubility of less than 60 g/l at 25 degrees C and optionally (iii) 0-5 wt% at least one monounsaturated monomer (C) with at least one ionic and/or ionisable functional group, (iv) 0-10 wt% monomer(s) with at least two ethylenic bonds, and (v) 0-20 wt% monounsaturated monomer(s) different from (A) and (C) with a water-solubility. Also claimed are copolymer dispersions obtained by this process, and their applications.

Description

Contain the water-soluble monomer of N-vinyl and the aqueous copolymer dispersion of hydrophobic monomer

The present invention relates to a kind of preparation method of aqueous copolymer dispersion, it is to obtain by free radical water emulsion polymerization containing the non-ionic water-soluble monomer (monomer A) of N-vinyl and the monomer mixture of hydrophobic monomer basically.

The existing water miscible monomer of N-vinyl-functional and the multipolymer of hydrophobic monomer of containing of known per se.Usually they are at a kind of organic solvent, as contain the fatty alcohol of 1 to 4 carbon atom, or in alcohol/water mixture (for example referring to US-A4520179, US-A5319041 or EP-A418721), prepare by free radical solution polymerization.No matter yet be based on the consideration of cost, the requirement that still conforms better, the use of removing organic solvent all is basic interest places.

For the water miscible monomer of N-vinyl-functional and the radical copolymerization of hydrophobicity comonomer of containing, can in limited scope, use water as solvent and substitute organic solvent.For example DE-A 2218935 discloses the mode with aqueous solution polymerization, proceeds to many 30 weight %, the preferred radical copolymerization of the hydrophobic monomer N-vinyl pyrrolidone of 15 weight % at the most.WO93/18073 discloses the aqueous solution polymerization of N-vinyl lactam, and based on the total amount of polymerization single polymerization monomer, the ratio of hydrophobic monomer equally also is restricted to less than 30 total amount %.

By the method for free radical water emulsion polymerization, should obtain the higher polymkeric substance of hydrophobic monomer content on the principle.Yet DE-A4139963 and WO93/15120 are mentioned to, and contain the free radical water emulsion polymerization greater than the monomer mixture of the vinyl pyrrolidone of 10 weight %, will cause unsettled high viscosity dispersion, and this will cause separating tendency, and are difficult to reclaim.Thus, when the form preparation with copolymerization contains the monomeric aqueous polymer dispersions of a large amount of relatively water-soluble N-of containing vinyl-functional, then avoided in alcoholic solvent, and subsequently solvent has been changed to the free radical solution polymerization (for example referring to DE-A4139963) of water.Except that the above-mentioned shortcoming of making solvent with alcohols, should also be noted that not resemble water that alcohol will be got involved Raolical polymerizable as conditioning agent, therefore can not obtain the high-molecular weight multipolymer by this approach.

WO93/15120 discloses can be by carrying out the emulsion graft copolymer that free radical grafting obtains on water-soluble homopolymer or multipolymer, this water-soluble homopolymer or multipolymer are to be formed by the monomer of the water miscible N-of containing vinyl-functional in water miscible liquid.

US-A4167439 disclose can be in aqueous solvent N-vinyl pyrrolidone by radical polymerization 5～30 weight % that obtain, that contain copolymerized form, the non-ionic copolymer of the methyl methacrylate of the acrylamide of 15～60 weight % and 30～70 weight %.These multipolymers are known as the micro-emulsion polymerization thing, and their particle diameter is preferably 0.05～0.08 μ m.Yet in the polyreaction in aqueous medium, also there is its problem in the use of a large amount of relatively acrylamides, because in the dispersion that can obtain by this method, the amount of unpolymerized acrylamide is relatively very high, and this compound under a cloud be carcinogenic, or be hypersensitive at least.

DE-A4342281 discloses in water miscible liquid, substantially the polymerization of the monomer mixture of being made up of the N-caprolactam.Because polymkeric substance based on the N-caprolactam, when especially the content of the N-caprolactam of copolymerization is preferably greater than 90 weight %, the rising of its solubility with temperature in water and reducing, although this polymerization is carried out in water miscible liquid, cause polymkeric substance in water, can not obtain clear soln.This base polymer is not an object of the present invention.

Therefore the purpose of this invention is to provide a kind ofly in the reaction medium that constitutes by water basically,, prepare the method for multipolymer at least by the hydrophobic monomer B of water-soluble monomer A that contains the N-vinyl and 30 weight % by the radical polymerization of monomers B.

Have now found that,, can realize this purpose by using the free radical water emulsion polymerization of water-soluble polymerization initiator.

In view of the above, the invention provides the method that a kind of free radical water emulsion polymerization by unsaturated vinyl monomer prepares aqueous copolymer dispersion, this unsaturated vinyl monomer comprises: i) at least a non-ionic monomer A of 10～70 weight %, solubleness during 25 ℃ of this monomers in water is greater than 60g/l, and contain the N-vinyl, the ii) unsaturated hydrophobic monomer B of at least a mono-vinyl of 30～90 weight %, solubleness during 25 ℃ of this monomers in water is less than 60g/l, and if the words that need, the iii) at least a mono-vinyl unsaturated monomer C of 0～5 weight %, this monomer has at least one ion and/or ionizable functional group, the iv) at least a monomer D of 0～10 weight %, this monomer has at least 2 vinyl unsaturated link(age)s, the v) at least a other mono-vinyl unsaturated monomer E of 0～20 weight %, it is different from monomer A and C, and its solubleness in water is greater than 60g/l 25 ℃ the time, and this method comprises uses a kind of water miscible polymerization starter.The monomer A that below provides to the weight percentage of E is with respect to wanting polymeric monomer total amount.

The present invention also provides the polymeric dispersions that can be obtained by method of the present invention.

Generally speaking, the solubleness of used initiator in water is very big, to such an extent as to used initiator is dissolved in separately the reaction medium fully.Preferred polymerization starter comprises water miscible azo compound; as 2; 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl)] propane, 2,2 '-azo two (2-amidine propane) and their acid salt; hydrochloride particularly; acetate or sulfuric acid (hydrogen) salt, 4,4 '-azo two (4-cyanopentanoic acid) and its basic metal or ammonium salt; sodium salt particularly, 2-(formamyl azo) isopropyl cyanide.They also comprise water miscible superoxide and hydroperoxide, as tertbutyl peroxide, and t-amyl peroxy hydrogen, cumyl hydroperoxide, pinane hydrogen peroxide, peroxidation pyrosulfuric acid and salt thereof, particularly its basic metal or ammonium salt, and hydrogen peroxide.These superoxide and hydroperoxide can use separately, or preferably, use with reductive agent, reductive agent for example is the salt of methylol-sulfinic acid or xitix, or can be multiple in the aqueous solution transistion metal compound that exists of oxidation state, for example iron (II) salt or copper (II) salt (being called redox initiation system).Particularly preferred initiator is above-mentioned water-soluble azo compounds, especially exist with the form of salt or can shape salifiable those, the salt of peroxidation pyrosulfuric acid, and hydrogen peroxide, the initiator of back preferably use with iron (II) salt or copper (II) salt.

Based on the total amount of wanting the polymeric monomer A to E, the amount that is used for the polymeric initiator is preferably 0.02～15 mole of %, and especially 0.05～10 mole of % particularly preferably is 0.1～3 mole of %.When above-mentioned azo-compound when the initiator, the amount of initiator is preferably less than 1 mole of %, and superoxide and hydroperoxide are during as polymerization starter, the preferred amount of using is bigger.Preferably, polymerization starter joins in the polyreaction with the form of dissolving or dilution.The suitable solvent is above-mentioned C1～C4 alcohols and/or water, preferably makes water as unique solvent and/or thinner.The initiator content of these solution is preferably 0.2～20 weight %, particularly 0.5～10 weight %.

Initiator can be included in the starting polymerization mixture, or speed that can its consumption is added.In a preferred embodiment of the invention, at least 70%, especially at least 80%, particularly preferably be at least 90% initiator form with water or water-alcohol solution, add in the polyreaction continuously.A spot of initiator, preferably at least 1%, especially at least 2%, particularly preferably be at least 5% initiator, be included in initial the feeding intake that adds reactor, so that polyreaction begins.

The reaction medium that is used for free-radical emulsion polymerization is water and is no more than 20 weight % usually based on the amount of reaction medium, preferably is no more than 10 weight %, especially be no more than one or more C1～C4 alcohol of 5 weight % content, as methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol or isopropylcarbinol.Particularly preferably be with water as unique reaction medium.Polymerization is normally almost being carried out under the neutral pH value, and preferred pH value is 5 to 9.The pH value can be by adding alkali, and as ammonia or sodium hydroxide, perhaps sour, example hydrochloric acid or sulfuric acid are regulated or kept.Or polymerization can be carried out in the presence of suitable buffer reagent, and buffer reagent for example is bicarbonate of ammonia, hydrophosphate, borate, acetate, Citrate trianion, succinate, glycinate or phthalate.Preferred organic buffer reagent, but bicarbonate of ammonia particularly.

Want the polymeric monomer in aqueous reaction medium, to be introduced at the beginning (batch technology) in the reactor.Yet polymerization is preferably undertaken by charging technology.Be meant by this technology, with the major part of polymerization single polymerization monomer, especially at least 70%, particularly preferably be 75～90%, be metered in the starting polymerization mixture, if need, with the form of water or water-alcohol solution or water miscible liquid.

Under the situation of charging technology, polymerization starter or can be included in reactor initial reinforced perhaps can above-mentioned mode be metered in the starting polymerization mixture.Preferably, initiator is added continuously and with monomer abreast.Particularly preferably be, the monomer and the initiator in water or water-pure reaction medium of above-mentioned part are introduced when initial, make it rise to temperature of reaction then.Usually the monomeric reinforced time is 0.5 to 14 hour, preferred 1 to 12 hour, and preferred especially 2 to 10 hours.The reinforced time of initiator is identical, or preferably more longer.

Temperature of reaction is generally 60～90 ℃, but can be up to 130 ℃.Reaction can be carried out under barometric point, if or use the pyritous words, under himself vapor pressure, or in that being higher than under the atmospheric pressure of causing carried out by using rare gas element.Nitrogen is particularly suitable for doing rare gas element.

Polymerization also can be passed through high-energy radiation, causes as gamma-rays, or can photopolymerisable form carry out; Promptly in the presence of suitable water-soluble light trigger, cause by visible light or ultraviolet ray.Shi Yi light trigger comprises methyl phenyl ketone especially, and the soluble derivative of benzophenone or thioxanthone, these derivatives have the functional group that increases its solubleness in water usually, as hydroxyl, and carboxyl, nitro or amino.

Preferably, after polymerization, also has a post polymerization process, to finish monomeric conversion.This means, after monomer/polymerization starter has added, in the starting polymerization mixture, add to form the initiator of free radical again, and if need, the temperature of reaction mixture is risen on the actual polymerization temperature.The initiator of suitable post polymerization process is above-mentioned initiator, and percarbonate or peroxyesters.Preferably, superoxide and/or the hydroperoxide of mentioning are used with reductive agent and/or transition metal (seeing above-mentioned).The post polymerization process is directly followed after monomers/initiator has been added usually and is carried out, or carrying out afterwards in 4 hours at the most after monomers/initiator has been added.The required initiator of post polymerization process can disposablely add, or adds in to 10 hours last.For the post polymerization process, another feasible program is to add continuously twice or more times initiator.

Can carry out the physics aftertreatment to the dispersion of gained after polymerization or the post polymerization process: for example steam distillation or carry out stripping with rare gas element such as nitrogen.This will remove the impurity of steam-volatile from dispersion, as the monomer of remnants.

The polymkeric substance that obtains by polymerization process of the present invention has higher relatively molecular weight usually.If need lower molecular weight, then can obtain by in initial polyblend, adding conditioning agent.

The example of suitable conditioning agent is an aldehyde, as formaldehyde, and acetaldehyde, propionic aldehyde, butyraldehyde-n and isobutyric aldehyde, formic acid, ammonium formiate, oxammonium sulfate and phosphatic hydroxylamine.Also can use the conditioning agent that contains the sulphur that organic formal bond closes.The example of these conditioning agents is the di-n-butyl thioether, di-n-octyl thioether or diphenylsulfide, diisopropyl disulfide thing, di-n-butyl disulphide, di-n-hexyl disulphide or diacetyl disulphide and di-t-butyl trisulphide.Preferably, conditioning agent contains the sulphur of SH base form.The example of this class conditioning agent is a normal-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan.Particularly preferably be water miscible sulfur-bearing polymerization regulator, as hydrosulphite, dithionite and as sulfo-glycolic acid ethyl ester, thioserine, 2 mercapto ethanol, 1, the 3-mercaprol, 3-sulfydryl propane-1,2-glycol, 1,4-sulfydryl butyleneglycol, Thiovanic acid, 3-thiohydracrylic acid and mercaptosuccinic acid, thioglycerol, di-alcohol thioether, the sulfo-glycol ether, ethylenebis dithiocarbamate ethanol, the compound of thiocarbamide and dimethyl sulfoxide (DMSO).Other suitable conditioning agent is an allylic cpd, as vinyl carbinol or allyl group bromination thing, and benzyl compounds, as benzyl chloride, or alkyl halide, as chloroform, bromination trichloromethane or tetracol phenixin.In an embodiment preferred, conditioning agent itself is metered in the reaction mixture, or its solution at water and/or C1～C4 alcohol is metered in the reaction mixture.

If need, in the enforcement of the inventive method, can use the surfactant that is generally used for letex polymerization, in other words be emulsifying agent and/or protective colloid.When using surfactant, based on wanting the monomeric amount of polymeric, its consumption is generally 20 weight % at the most, preferred 0.5～10 weight %, especially 1～5 weight %.Suitable surface active cpd comprises protective colloid and neutral, negatively charged ion or cationic emulsifier.Especially, suitable anionic emulsifier comprises the alkali metal salts or ammonium salt of relative longer chain fatty acid, the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation (EO unit: 4 to 30, alkylphenol (the E0 unit: 3 to 50 of alkyl: C10～C22) and ethoxylation, the alkali metal salts or ammonium salt of the sulfuric acid monoester of alkyl: C4～C10), alkylsulphonic acid (alkali metal salts or ammonium salt of alkyl: C12～C18), and the alkyl aryl sulphonic acid (alkali metal salts or ammonium salt of alkyl: C9～C18).Spendable other anionic emulsifier is an alkali metal salt of dialkyl sulfosuccinate, an alkali metal salt of alkyl naphthalene sulfonic acid and naphthene sulfonic acid.Also can use cationic active compounds, as the aliphatic amide quaternary ammonium salt, alkyl pyridine quaternary ammonium salt (C8～C30), N-alkyl morpholine quaternary ammonium salt (C8～C30) or alkylation tetrahydroglyoxaline.

Other has the auxiliary agent (cosolvent) of emulsifying effect to add with emulsifying agent, and based on monomeric amount, its consumption is at most 20 weight %, preferred 0.5～10 weight %, especially 1～5 weight %.Suitable cosolvent comprises the aliphatic series of linearity or branching or cyclic aliphatic C1～C30 alcohol and composition thereof, as propyl carbinol, and n-hexyl alcohol, hexalin, 2-Ethylhexyl Alcohol, isooctyl alcohol, n-Octanol, nonylcarbinol, n-dodecane alcohol, Stearyl alcohol, oleyl alcohol and cholesterol.Other cosolvent is C4～C20 alkane diol, has 1 to 4 unitary ethylene glycol alkyl oxide of oxidation ethylidene, as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether or tetraethyleneglycol dimethyl ether, and N-alkyl pyrrolidone, each alkyl chain have the N-alkyl of 1 to 8 carbon atom-and N, the N-dialkyl acetamides, its example is a N-Methyl pyrrolidone, N-hexyl pyrrolidone, diethyl acetamide and N-octyl group ethanamide.

Method of the present invention is particularly suitable for preparing the total amount based on wanting polymerization single polymerization monomer, contains 20～60 weight %, the particularly aqueous polymer dispersions of the monomer A of the copolymerized form of 30～60 weight %.The N-vinyl lactam of preferred 6 to 8 carbon atoms of monomer A, as the N-vinyl pyrrolidone, N-vinyl piperidone, N-caprolactam, and/or the acyclic N-vinyl carboxamide of 2 to 6 carbon atoms, as N-vinyl formamide or N-methyl-N-vinyl acetamide.Particularly preferred monomer A is the N-vinyl lactam.The N-vinyl imidazole is suitable for doing monomer A too.In a preferred embodiment of the present invention, the solubleness of monomer A in water is greater than 100g/l (25 ℃).

Usually, suitable monomer B for all can with the hydrophobic monomer of monomer A copolymerization, and 25 ℃ of its solubleness in water are less than 60g/l.Especially, they comprise the C1～C10 alkyl ester, particularly vinylformic acid of the unsaturated C3 of mono-vinyl～C6 carboxylic acid and the ester of methacrylic acid and C1～C10 alkanol or C5～C10 cycloalkanol, and these alcohol for example are methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-butanols, the trimethyl carbinol, Pentyl alcohol, n-hexyl alcohol, 2-ethyl-hexane-1-alcohol, n-Octanol, nonylcarbinol, 2-propyl group-heptane-1-alcohol, hexalin, 4-tertiary butyl hexanol, or 2,3,5-trimethylammonium-hexalin.Other suitable monomer B is the two C1～C10 alkyl ester of vinyl unsaturated dicarboxylic acid, toxilic acid for example, and fumaric acid or methylene-succinic acid and above-mentioned C1～C10 alkanol or C5～C10 cycloalkanol, its example is dimethyl maleate or dibutyl maleinate.Vinyl aromatic compounds such as vinylbenzene and alpha-methyl styrene also are suitable for doing monomers B, and their aromatic nucleus can non-replacement or is replaced by one or more substituting groups, these substituting groups are selected from C1～C4 alkyl, halogen, chlorine particularly, and/or hydroxyl, these substituting groups also can be further by ethoxylation.Monomers B also comprises vinyl, allyl group and the methacrylic ester of the aliphatic carboxylic acid of the linearity of 2 to 20 carbon atoms or branching in addition, as acetic acid, and propionic acid, butyric acid, valeric acid, caproic acid, 2 ethyl hexanoic acid, capric acid, lauric acid and stearic vinyl acetate, and corresponding allyl ester and methyl allyl ester.In addition, suitable monomer B is vinyl, allyl group and the methallyl ether of the fatty alcohol of the linearity of 2 to 20 carbon atoms or branching, as methyl, and ethyl, dodecyl, the vinyl ether of hexadecyl and octadecyl.Preferably, the consumption of monomers B is 40～70 weight %, particularly 40～60 weight %.

Have the suitable monomer C of at least one ion and/or ionizable functional group, comprise negatively charged ion or acid monomer and cationic monomer.Preferably, the consumption of monomer C is 5 weight % at the most, and 3 weight % at the most particularly are under the situation of acid monomer, based on the amount of free acid.Especially, Shi Yi negatively charged ion or acid monomer comprise the compound that contains a carboxyl, sulfo group and/or phosphono group in those molecules at least.Suitable negatively charged ion and acid monomer comprise the unsaturated C3 of vinyl～C6 monocarboxylic acid respectively, as vinylformic acid, methacrylic acid or butenoic acid, the unsaturated C4 of vinyl～C8 di-carboxylic acid, toxilic acid, fumaric acid, methylene-succinic acid or first are for propanedioic acid, with the monoesters of described C4～C8 di-carboxylic acid and C1～C10 alkanol, as monomethyl maleate, the positive butyl ester of toxilic acid list; The vinyl unsaturated sulfonic acid, as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-3-methyl propane sulfonic acid and 2-methacryloyl amido-2-methyl propane sulfonic acid, and unsaturated phosphonic acids of vinyl such as vinyl phosphonate.Preferably, use these acid with the form of its salt.Suitable gegenion comprises alkalimetal ion and alkaline-earth metal ions, as sodium ion, and potassium ion or calcium ion, and ammonium ion.In a preferred embodiment of the present invention, before polymerization, change free acid into anionic form by suitable alkali, preferably, with the form of water or water-alcohol solution.Suitable alkali comprises above-mentioned alkali-metal oxyhydroxide and carbonate, calcium hydroxide, ammonia and organic amine, pyridine and amidine.Especially, suitable organic amine is included in, two or the trialkanolamine that 2 to 5 carbon atoms are arranged on the chain triacontanol base, as one, two or trolamine, and one, two or three (different) Propanolamines or 2-amino-2-methyl propane; The alkanediol amine that 2 to 4 carbon atoms are arranged on the alkanediol base, as 2-amino-2-methyl-1, ammediol or 2-amino-2-ethyl-1, ammediol; The many hydramine of alkane, as two (2-ethylhexyl) amine, three amylamines or lauryl amine, and amino ethers are as morpholine.

Suitable cationic monomer C comprises the undersaturated N of the containing compound of vinyl, N-vinyl imidazole class for example, as the N-vinyl imidazole, 2-methyl isophthalic acid-vinyl imidazole, 2-ethyl-1-vinyl imidazole, 4-methyl isophthalic acid-vinyl imidazole or 5-methyl-N-vinyl imidazole, N-vinyl imidazole quinoline class, 2-, 3-or 4-vinylpridine, they have changed the form of quaternary ammonium salt into by alkylation.

Suitable alkylating reagent comprises alkyl chloride, as monochloro methane, and a monobromethane and a methyl iodide, monochlorethane, a chloropropane, benzyl chloride or bromotoluene; Also can be sulfuric acid dialkyl, particularly methyl-sulfate and ethyl sulfate, and the alkylidene oxide in the presence of acid, as oxyethane, propylene oxide.Preferred alkylating reagent is monochloro methane, methyl-sulfate and ethyl sulfate.Cationic monomer C also comprises the diallyl amine compound, as dimethyl diallyl ammonium chloride, and diethyl allyl ammonium chloride or the pyridine of diallyl bromination base.Other compound that can be used as cationic monomer C is the ester of the aminoalkanol of the unsaturated C3 of vinyl～C6 carboxylic acid and general formula I, or the acid amides of the amine of vinyl unsaturated carboxylic acid and general formula I I, Wherein R is C2～C5 alkylidene group, and R1, R2 and R3 are respectively CH3, C2H5 or C3H7, and X θ is the negatively charged ion of mineral acid, as chlorion, and anion of carboxylic acid, or be methosulfate or ethosulfate.

Polymeric dispersions of the present invention also can use the monomer D that is called cross-linking monomer, and the monomer that in other words promptly has two vinyl unsaturated link(age)s at least prepares.Special suitable monomer D comprises the dibasic ester or the polynary ester of the unsaturated C3 of binary or polyvalent alcohol and vinyl～C6 carboxylic acid.The example of this compounds is the binary alcohol esters of diacrylate and dimethacrylate, as two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid 1,3-or 1, the 4-butanediol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid triglycol ester, two (methyl) vinylformic acid TEG ester, two (methyl) vinylformic acid 1,12-dodecane alcohol ester, the many glycol esters of two (methyl) vinylformic acid, 2, two (right-(methyl) acryloxy phenyl) propane of 2-, two (methyl) vinylformic acid tripropylene glycol ester, trimethoxy propane three (methyl) acrylate, three (methyl) vinylformic acid pentaerythritol ester or four (methyl) vinylformic acid pentaerythritol ester.Other suitable monomer D is vinyl, allyl group and the methacrylic ester of the unsaturated C3 of vinyl～C6 carboxylic acid, as (methyl) vinyl acrylate, allyl ester and methacrylic ester, aliphatic series or aromatic dicarboxylate's vinyl, allyl group and methacrylic ester, as phthalic acid divinyl ester or diallyl phthalate, the polynary acid amides of vinyl unsaturated carboxylic acid, N particularly, N '-methylene diacrylamine, N, N '-butylidene diacrylamine, diacrylamine guanidine-acetic acid methyl esters, terephthalylidene tetrapropylene acid amides.Other compound that can be considered as monomer D is a divinyl aromatic compound, as Vinylstyrene, also can be divinyl, diallyl or the dimethyl-allyl derivative of urea and/or imidazolone, as N, N '-divinyl urea and N, N '-divinyl imidazolidine-1-ketone.Preferably, the consumption of monomer D is 5 weight % at the most, preferably 2 weight % at the most.

Suitable monomer E is not for containing the neutral water soluble monomers of N-vinyl.They comprise vinyl cyanide, above-mentioned C3～C6 carboxylic acid hydroxy alkyl ester, as (methyl) Hydroxyethyl acrylate, 2-or 3-hydroxypropyl acrylate or 4-hydroxy butyl ester, the acid amides and the N-methylol amide of the unsaturated C3 of vinyl～C6 carboxylic acid, as acrylamide and Methacrylamide, and the acid anhydrides of the unsaturated C4 of vinyl～C6 di-carboxylic acid, as maleic anhydride.Preferably, the consumption of monomer E is 10 weight % at the most.

In a preferred embodiment of the present invention, polymerization is to carry out under the situation of monomer-free C.In view of the above, the polymeric monomer mixture to have following composition :-10～70 weight %, preferred 20～60 weight %, the monomer A of 30～60 content % particularly ,-30～90 weight %, preferred 40～80 weight %, the monomers B of 40～70 weight % particularly,-0～10 weight % are preferably less than 5 weight %, particularly less than the cross-linking monomer D of 2 weight %,-0～20 weight %, especially less than 10 weight %, particularly preferably be the water-soluble monomer E that tries one's best few, monomer E is different with monomer A.

Particularly preferably, want the polymeric monomer mixture only to contain monomer A and B in this embodiment.

In this case, can prepare polymkeric substance having or do not have under the surface active cpd.Usually preferred no surface active cpd is when particularly the solubleness of hydrophobic monomer B in water is greater than 10g/l.Yet when for implementing institute when essential, this class monomer mixture also can carry out polymerization in the presence of mentioned emulsifier and/or protective colloid.

In another embodiment of the present invention, in the presence of ion or ionizable monomer C, carry out monomer A and B, and if ticket body D that needs and the polymerization of E.Based on wanting polymeric monomer total amount, the consumption of monomer C is preferably 0.1～10 weight %, and especially 0.2～5 weight % particularly preferably is 0.5～3 weight %.But monomer C stabilization of polymer therefore can be without emulsifying agent and/or protective colloid in emulsion polymerization process.Yet, when also can in polyreaction, adding this class surface active cpd when required with above-mentioned amount for implementing.Although can be like this, but the preparation method of preferred surfactant-free.The amount of monomer A, B, D and E as mentioned above.Under the situation of this embodiment, preferred monomer mixture only contains monomer A to C.

The polymeric dispersions that can be got by the inventive method is new, and also can provide this polymeric dispersions by the present invention.Based on the gross weight of dispersion, the solid content of these polymeric dispersions is generally 10～60 weight %, preferred 15～40 weight %.The transmittance (based on the extent of dilution of 0.5 weight %, path length is 1cm) of the polymeric dispersions that can get according to the present invention is generally greater than 50%, is preferably greater than 70%.The particle diameter of dispersive polymer particle is preferably greater than 100nm usually greater than 50nm.Here selected parameter is the weighed average of particle diameter, and it can pass through ultracentrifugal analysis, presses W.Scholtan and H.Lange, and the method for Colloid-Z.und Z.Polymere 250 (1972) 782-796 is measured.

The polymkeric substance that can get according to the present invention has higher molecular weight usually, and (Volume 13 for H.Fikentscher, Zellulose-Chemie, (1932) 58-64 corresponding to Fikentscher K value; Be to measure with the ethanolic soln of the polymkeric substance of 1 weight % intensity) for greater than 50, be preferably greater than 70, be preferably greater than 80 especially.By using conditioning agent also can obtain lower molecular weight.Even in this case, weight-average molecular weight Mw is greater than 30 usually also greater than 50000 corresponding to Fikentscher K value.

Polymeric dispersions by the inventive method can get if need, can change it into pressed powder by the drying means of prior art.Do not select lyophilize for use, especially, suitable drying means comprises spraying drying, bed spray drying, drum drying and belt drying.In many application scenarios, suggestion changes aqueous polymer dispersions into solid form by the evaporation forcing machine.

The polymkeric substance that can be got by the inventive method is used as thickening material on the one hand in aqueous medium, can form water-solubility membrane on the other hand.They can be used as the auxiliary agent of medical treatment, makeup or chemurgy batching, and can prepare paint and coating composition, sizing material and tackiness agent.Especially, they are used for makeup and medicine batching, as making additive or vehicle at lacquer, the qualitative goods of hair or hair spray; In the preparation of skin cosmetic, for example make skin adhesive glue or immune chemical-as catheter coatings.The special applications of polymkeric substance of the present invention in medical treatment comprises, makes wet or dry adhesives with them, makes sustained release dosage in the coating of matrix or slowly-releasing batching, makes the gel formation body, promptly releases coating and film coalescence aid.The polymkeric substance that makes by the present invention also can be used as the auxiliary agent of agricultural chemicals; For example make the batching that seed coating or soil discharge fertilizer, or in the preparation of granular fish food, make auxiliary agent.

Because the polymkeric substance of pressing the present invention's preparation is to organic and strong dissemination mineral dye, polymkeric substance of the present invention is suitable for doing following reagent, and as or rust cleaning antirust in the metallic surface, antiscale or scale removal are made dispersion agent in the dyes/pigments dispersion, as in printing ink.As reference ground, polymkeric substance of the present invention can be used for ink jet recording medium, ink slurry and ballpoint pen oil.

Interest for application point also shows polymkeric substance of the present invention and organic compound (for example, lower hydrocarbon, phenol, tannin and various oxidation inhibitor), enzyme and protein, or other organic polymer form strong hectare of title complex to.Polymkeric substance of the present invention also with mineral compound, particularly hydrogen peroxide, halogenide, metal-salt form title complex.Correspondingly, polymkeric substance of the present invention can be removed tannin from aqueous medium in ion exchange material, phenol, protein or polyvalent cation, stable peroxide hydrogen in sterilizing agent, or for example in sanitas, stablize oxidation inhibitor, the polymkeric substance as metal complexes in the reversible absorption of oxygen is total to part, or catalyzer.Polymkeric substance of the present invention in addition also can be used for the stable metal colloid.As with reference to ground, the precious metal nuclei of crystallization when polymkeric substance of the present invention can be used as precipitated silver, and as the stablizer of silver halide emulsion.

Polymkeric substance of the present invention also is suitable for improving surface or interface performance.Based on they modifying functions to the surface, goods of the present invention for example can be used as the coating of polyolefine, glass and glass fibre.Because their surfactivity, they also can be used as metallic colloid for example in stable or free radical water emulsion polymerization in protective colloid.As with reference to ground, polymkeric substance of the present invention can be used as by the auxiliary agent that reclaims oil in the butyraceous water, in the extraction of oil or Sweet natural gas as auxiliary agent, and in the transportation of oil and natural gas as auxiliary agent.Other Application Areas that polymkeric substance of the present invention is found has, and as auxiliary agent, no matter be as flocculant aid, still removes paint and irreducible oil in waste water in waste-water purification.Polymkeric substance of the present invention also can be used as phase-transfer catalyst and improves the material of solubleness.

Polymkeric substance of the present invention also can be used on polyolefinic painted on, painted mixed inhibitor as diffusive migration thing material, the adhesion promotor of dyestuff, the auxiliary agent in imprint lithography, photoimaging and the diazonium-type method, the auxiliary agent in metal casting and the tempering, the auxiliary agent of metal quenching bath, auxiliary agent in the gasometry, the composition of ceramic binder, the paper making additive of special paper, tackiness agent in the painted paper pulp, the binder constituents in the plaster bandage.

In addition, polymkeric substance of the present invention also is suitable for use as proton conductor, and for example is used for conductive coating in the charge transfer negative electrode, for example is used as solid electrolyte in the lithium cell at solid state battery.Polymkeric substance of the present invention also can be used for preparing contact lens, synthon, air filter such as cigarette filter or film.Polymkeric substance of the present invention also can be applicable to refractory layer, heat-sensitive layer and thermistor.

Following embodiment will further specify the present invention, but not limit it.Embodiment: I. analyze

Measure the K value of polymkeric substance by viscosity apparatus, its method as described in the H.Fikent scher (referring to H.Fikentscher, Zellulose-Chemie, 13, (19 32) 58-64 and " chemical encyclopedia ", the 2nd edition, Kirk Othmer, Wiley﹠Sons, 1970, pp.427-428).It is with the dispersion samples drying, and by the ethanolic soln of the polymer manufacture 1 weight % intensity of gained by respectively.

The mensuration of transmittance is by respectively dispersion samples being diluted with deionized water, to solid content be 0.5 weight %, measure transmittance with the light path of 1cm then.

Residual monomer content is by gas chromatography determination.II. the preparation of copolymer dispersion of the present invention (embodiment 1 to 20) embodiment 1

The dispersion that contains 30 weight %N-vinyl pyrrolidones and 70 weight % vinyl acetates.

To being furnished with agitator, reflux exchanger adds following mixture in the reactor of gas introduction tube and two opening for feeds that are separated from each other:

20 gram N-vinyl pyrrolidones,

50 gram vinyl acetates,

5 gram initiator streams 1 and

1000 gram water.

This starting material added with nitrogen and be heated to 70 ℃ of initial temperatures.Subsequently, when keeping this temperature, monomer body streams and initiator streams 1 are added in 8 hours with constant speed simultaneously.Ammonia solution with dilution in the polymeric process is adjusted to 6～7 with the pH value of reaction soln.Internal temperature is risen to 75 ℃ then, in 6 hours, add initiator streams 2 when keeping this temperature.Continuation with temperature remain on 75 ℃ 2 hours.Subsequently reaction mixture is carried out steam distillation.Collect 100 gram overhead products approximately, solid content is adjusted to about 20 weight %.Obtaining the K value thus is 95, and solid content is 19.5 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 130ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.

The monomer materials flow: 70 gram N-vinyl pyrrolidones,

160 gram vinyl acetates

Initiator streams 1:1 gram 2,2 '-solution of azo two (2-amide group propane) dihydrochloride in 100 gram water

Initiator streams 2:1 gram 2,2 '-solution of azo two (2-amide group propane) dihydrochloride in 100 gram water

Ammonia solution with dilution is adjusted to 6 with the pH value of starting material and initiator streams 1 and 2.Embodiment 2

The dispersion that contains 30 weight %N-vinyl pyrrolidones and 70 weight % vinyl acetates.

To being furnished with agitator, reflux exchanger adds following mixture in the reactor of gas introduction tube and two opening for feeds that are separated from each other:

20 gram N-vinyl pyrrolidones,

50 gram vinyl acetates,

6 gram bicarbonate of ammonia,

5 gram initiator streams 1 and

1000 gram water.

Polymerization process is identical with embodiment's 1.In polymerization process, pass through to add the pH value maintenance constant (pH5～7) of buffer reagent (bicarbonate of ammonia) with reaction soln.Obtaining the K value thus is 98, and solid content is 19.7 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 70ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.

The monomer materials flow: 70 gram N-vinyl pyrrolidones,

160 gram vinyl acetates

Initiator streams 1 and 2 identical with embodiment 1.Embodiment 3

The dispersion (method of regulation) that contains 30 weight %N-vinyl pyrrolidones and 70 weight % vinyl acetates.

As described in embodiment 1, carry out polymerization.As different from Example 1, the monomer materials flow also contains 2 gram allyl alcohols.

Obtaining the K value thus is 72, and solid content is 19.1 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 550ppm, has fade faint yellow.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.Embodiment 4

The dispersion (method of regulation) that contains 30 weight %N-vinyl pyrrolidones and 70 weight % vinyl acetates.

As described in embodiment 1, carry out polymerization.As different from Example 1, the monomer materials flow also contains 0.5 gram mercaptoethanol.Obtaining the K value thus is 72, and solid content is 19.1 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 550ppm, has fade faint yellow.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.Embodiment 5

The dispersion (method of regulation) that contains 20 weight %N-vinyl pyrrolidones and 80 weight % vinyl acetates.

To being furnished with agitator, reflux exchanger adds following mixture in the reactor of gas introduction tube and two opening for feeds that are separated from each other:

15 gram N-vinyl pyrrolidones,

50 gram vinyl acetates,

5 gram initiator streams 1 and

1000 gram water.

Polymerization process and initiator streams 1 and 2 identical with embodiment 1.Obtaining the K value thus is 61, and solid content is 20.3 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 200ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.

The monomer materials flow: 45 gram N-vinyl pyrrolidones,

190 gram vinyl acetates,

2 gram allyl alcohols.

Initiator streams 1 and 2 identical with embodiment 1.Embodiment 6

The dispersion (negatively charged ion product) that contains 60 weight %N-vinyl pyrrolidones and 40 weight % tert-butyl acrylates.

To being furnished with agitator, reflux exchanger adds following mixture in the reactor of gas introduction tube and three opening for feeds that are separated from each other:

50 gram N-vinyl pyrrolidones,

0.6 restrain the CuIICl2 solution of 0.01 weight % intensity,

5 gram initiator streams 1 and

1000 gram water.

This starting material is heated to 70 ℃ under nitrogen, and with monomer body streams 1 and 2 and the initiator streams in 8 hours, add simultaneously with constant speed.Subsequently temperature is remained on 75 ℃ 6 hours.Obtaining the K value thus is 78, and solid content is 19.4 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 50ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.

Monomer materials flow 1:130 gram N-vinyl pyrrolidone,

120 gram tert-butyl acrylates

Monomer materials flow 2:3.0 gram sodium hydroxide neutral vinylformic acid,

50 gram water

Initiator streams: the solution (30 weight %) of 10 gram hydrogen peroxide in 50 gram water.Embodiment 7

The dispersion (negatively charged ion product) that contains 60 weight %N-vinyl pyrrolidones and 40 weight % tert-butyl acrylates.

Polymerization process and monomer materials flow are identical with embodiment's 6, and the initiator streams contains the 20 gram superoxols (30 weight %) that are dissolved in the 50 gram water.Obtaining the K value thus is 62, and solid content is 20.0 weight %, and residual monomer N-vinyl pyrrolidone content is less than the dispersion white of 50ppm, that deposition is stable.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.Embodiment 8

The dispersion (method of regulation) that contains 60 weight %N-vinyl pyrrolidones and 40 weight % tert-butyl acrylates.

To being furnished with agitator, reflux exchanger adds following mixture in the reactor of gas introduction tube and two opening for feeds that are separated from each other:

50 gram N-vinyl pyrrolidones,

5 gram initiator streams 1 and

1000 gram water.

Polymerization process is identical with embodiment's 1.Obtaining the K value thus is 79, and solid content is 19.9 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 70ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.

The monomer materials flow: 130 gram N-vinyl pyrrolidones,

120 gram tert-butyl acrylates,

1 gram mercaptoethanol

Initiator streams 1:1 gram 2,2 '-azo two (2-amide group propane) dihydrochloride and the solution of 3.0 gram vinylformic acid in 100 gram water, neutralize with sodium hydroxide

Initiator streams 2:1 gram 2,2 '-solution of azo two (2-amide group propane) dihydrochloride in 100 gram water.Embodiment 9

The dispersion (method of regulation) that contains 60 weight %N-vinyl pyrrolidones and 40 weight % tert-butyl acrylates.

Polymerization process, monomer materials flow and initiator streams are identical with embodiment's 8, and the monomer materials flow contains 9 gram mercaptoethanols.Obtaining the K value thus is 50, and solid content is 19.0 weight %, and residual monomer N-vinyl pyrrolidone content is less than dispersion white, that deposition is stable of 50ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.Embodiment 10

The dispersion (negatively charged ion product) that contains 60 weight %N-vinyl pyrrolidones and 40 weight % tert-butyl acrylates.

To being furnished with agitator, reflux exchanger adds following elder brother's compound in the reactor of gas introduction tube and two opening for feeds that are separated from each other:

50 gram N-vinyl pyrrolidones,

5 gram initiator streams 1 and

1000 gram water.

Polymerization process is identical with embodiment's 1.Obtaining the K value thus is 38, and solid content is 20.3 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 300ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.

The monomer materials flow: 121 gram N-vinyl pyrrolidones,

120 gram tert-butyl acrylates,

Initiator streams 1:1 gram 2,2 '-azo two (2-amide group propane) dihydrochloride and 9.0 grams are as the solution of 3-methyl isophthalic acid-vinyl imidazole methylsulfuric acid ester in 100 gram water of neutralization solution,

Initiator streams 2:1 gram 2,2 '-solution of azo two (2-amide group propane) dihydrochloride in 100 gram water.Embodiment 11

The dispersion (negatively charged ion product) that contains 60 weight %N-vinyl formamides and 40 weight % tert-butyl acrylates.

To being furnished with agitator, reflux exchanger adds following elder brother's compound in the reactor of gas introduction tube and two opening for feeds that are separated from each other:

50 gram N-vinyl formamides,

5 gram initiator streams 1 and

1000 gram water.

Polymerization process is identical with embodiment's 1.Obtaining the K value thus is 56, and solid content is 19.4 weight %, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 350ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.

The monomer materials flow: 130 gram N-vinyl formamides,

120 gram tert-butyl acrylates,

Initiator streams 1:1 gram 2,2 '-azo two (2-amide group propane) dihydrochloride and the 3.0 gram solution of sodium hydroxide neutral vinylformic acid in 100 water,

Initiator streams 2:1 gram 2,2 '-solution of azo two (2-amide group propane) dihydrochloride in 100 gram water.Embodiment 12

The dispersion (dispersion that contains emulsifying agent) that contains 40 weight %N-vinyl pyrrolidones and 60 weight % methacrylic tert-butyl acrylates.

To being furnished with agitator, reflux exchanger adds following mixture in the reactor of gas introduction tube and two opening for feeds that are separated from each other:

10 gram Texapon ^NSO (sodium lauryl sulphate of ethoxylation),

In water 2.2 gram Sodium persulfates of 7% concentration,

0.8 gram bicarbonate of ammonia,

20 the gram monomer materials flows and

750 gram water.

This starting material added with nitrogen and be heated to 80 ℃ of initial temperatures.Subsequently, when keeping this temperature, monomer body streams and initiator streams 1 are added in 2 hours with constant speed simultaneously.With temperature remain on 80 ℃ 2 hours.Then initiator streams 2 is added and with temperature remain on 80 ℃ 1 hour; After initiator streams 3 adds, keep again 80 ℃ 3 hours.

Obtaining the K value thus is 48, and solid content is 28.8 weight %, and transmittance is 70.5%, and the pH value is 8.2, and residual monomer N-vinyl pyrrolidone content is dispersion white, that deposition is stable of 1500ppm.In ethanol, can obtain clearly solution by the sample of evaporation concentration gained.

The monomer materials flow: 180 gram methacrylic tert-butyl acrylates,

120 gram N-vinyl pyrrolidones,

0.6 gram 2-ethylhexyl mercaptoacetate (EHTG).

The aqueous solution of 7% concentration of initiator streams 1:9 gram Sodium persulfate.

Initiator streams 2:3.0 restrains hydrogen peroxide (solution of 30% concentration),

0.5 gram CuIICl2 (aqueous solution of 0.01% concentration)

Initiator streams 3:1.5 restrains hydrogen peroxide (solution of 30% concentration).Embodiment 13 to 20 (dispersion that contains emulsifying agent)

As described in embodiment 12, carry out polymerization.Used monomeric consumption and characteristic thereof are listed in the table 1.For monomer, used following abbreviation:

The VP=N-vinyl pyrrolidone

Oneself presses the VC=N-vinyl by interior acyl

T-BuMA=methacrylic tert-butyl acrylate

The i-BuMA=Propenoic acid, 2-methyl, isobutyl ester

The MMA=methyl methacrylate

Table 1

Embodiment	Monomer A [g] B[g]		Conditioning agent (EHTG) 1) [g]	K value 2)	LT3) [g]	SC4) [weight %]	pH	Residual monomer [ppm]
									????13	?VP?120	t-BuMA?180	????1.1	????41	?63.5	?30.6	?7.0	????VP ?2000
????14	?VP?60	t-BuMA?240	????0.6	????45	?66.5	?32.1	?7.6	????VP ?2000
									????15	?VP?60	?MMA?240	????0.6	????47	?82.0	?33.1	?7.8	?VP?500
????16	?VC?90	?t-BuMA?210	????0.6	????54	?77.0	?28.7	????- ????5)	VC?200
									????17	?VC?90	t-BuMA?21?0	????1.1	????38	?73.5	?28.6		VC?500
????18	?VC?120	t-BuMA?180	????1.1	????44	?93.0	?28.3		?VC?60
									????19	?VC?90	i-BuMA?210	????1.1	????43	?67.5	?35.2		VC?100
????20	?VC?60	?MMA?240	????1.1	????47	?76.0	?28.6		VC?300

1) EHTG: SC Fikent scher K value (seeing above-mentioned) 3 the 2-ethylhexyl mercaptoacetate 2)) transmittance (seeing above-mentioned) 4 of LT:1% concentration dispersion): value undetermined III solid content 5). the Application Example 21 of polymkeric substance of the present invention in the hair spray film forming matter

With known method, change the polymeric dispersions of embodiment 5,9,10 and 13 into polymer powder by spraying drying.

Dissolving 3 gram multipolymers in 62 gram ethanol and 35 gram glycol dimethyl ethers.Test gained hair spray batching on hair style, it shows splendid performance as hair cosmetic.Promptly release the additive that does not add other, they also show splendid typing effect.For further optimizing the performance of makeup, can also in batching, add well known to a person skilled in the art composition.IV polymkeric substance of the present invention is done the application of sustained release dosage in medication coat

At first prepare a pigment dispersion that contains following component:

0.5 parts by weight of titanium dioxide powder

4.0 weight part talcum

0.5 weight part food dye (Sicovit  red 30) and

7.0 weight parts water and with its homogenizing in silicon carbide disk mill.Add the water of 58 weight parts and the dispersion among the 30 weight part embodiment 1 then.The solid content of the dispersion of gained is 11 weight %.

In Aeromatic Strea (obtaining), 1745 these dispersions of gram are imposed in the 500 gram theophylline balls (0.8 to 1.3mm, and Spherofillin  is obtained by Knoll AG) by bed spray by Aeromatic.Inlet air temperature is 45 ℃, and air outlet temperature is 30 ℃.Air inlet speed is 100-130m3/h.With the speed of 8.5ml/min and the spray pressure of 0.8 crust, carry out spraying in 205 minutes continuously.In hot blast (60 ℃), carry out 5 minutes dryings then.

For measuring release conditions, the piller that applies is wrapped in (corresponding to the theophylline of each capsule 300mg) in the capsule, introduce the fluid (hydrochloric acid of 0.1N) in the 900ml mimic stomach in each capsule.In slurry formula instrument, under 37 ℃ and 50rpm, discharge test.After 2 hours, add the phosphate buffer enriched material, making the pH value is 6.8.

The release result is as follows:

2 hours-30.5%

4 hours-55.6%

6 hours-80.3%

8 hours-100.0%

These results that measured by ultraviolet spectrometer have demonstrated the percentage ratio of the theophylline that discharges.

Claims (12)

1. the free radical water emulsion polymerization by unsaturated vinyl monomer prepares the method for aqueous copolymer dispersion, and this unsaturated vinyl monomer comprises:

Solubleness when i) at least a non-ionic monomer A of 10～70 weight %, 25 ℃ of this monomers in water is greater than 60g/l, and contains the N-vinyl,

Solubleness when the ii) unsaturated hydrophobic monomer B of at least a mono-vinyl of 30～90 weight %, 25 ℃ of this monomers in water is less than 60g/l, and if need,

The iii) at least a mono-vinyl unsaturated monomer C of 0～5 weight %, this monomer has at least one ion and/or ionizable functional group,

The iv) at least a monomer D of 0～10 weight %, this monomer has at least 2 vinyl unsaturated link(age)s,

The v) at least a other mono-vinyl unsaturated monomer E of 0～20 weight %, it is different from monomer A and C, and 25 ℃ the time its solubleness in water greater than 60g/l,

This method comprises uses a kind of water miscible polymerization starter.

2. the process of claim 1 wherein that polymerization starter is selected from water miscible azo compound, the alkali metal salts or ammonium salt of peroxidation pyrosulfuric acid, and hydrogen peroxide.

3. the process of claim 1 wherein and have at least 70% initiator to join in the polyreaction continuously with the form of water or water-alcohol solution.

4. the process of claim 1 wherein and want at least 70 weight % of polymerization single polymerization monomer to join in the polyreaction continuously.

5. the process of claim 1 wherein that monomer A is selected from the N-vinyl lactam of 6 to 8 carbon atoms and the acyclic N-vinyl carboxamide of 3 to 6 carbon atoms.

6. the method for claim 1, wherein monomers B is selected from alkene, vinyl aromatic compounds, the monocarboxylic C1 of the unsaturated C3～C6 of mono-vinyl～C10 alkyl ester, two C1～C10 the alkyl ester of the unsaturated C4 of vinyl～C6 di-carboxylic acid, the linearity of 2 to 20 carbon atoms or the vinyl acetate of branched aliphatic carbonxylic acids and (methyl) allyl ester, the linearity of 2 to 20 carbon atoms or the Vinyl Ether of branched aliphatic alcohols and (methyl) allyl ethers.

7. the process of claim 1 wherein that monomer A is to want 20～60 weight % of polymerization single polymerization monomer amount.

8. the process of claim 1 wherein that polymerization carries out under emulsifier-free or protective colloid.

9. the aqueous copolymer dispersion that can make by the method for claim 1.

10. the water-based polymers dispersion of claim 9, its solid content is 10～60 weight %, particularly 15～40 weight %.

11. the aqueous copolymer dispersion of claim 9, wherein the weight average particle diameter of polymer particle is greater than 100nm.

12. the aqueous copolymer dispersion of claim 9, its Fikentscher K value is greater than 50, particularly greater than 70.