TW201114781A - Process for preparing (alkoxy) polyalkylene glycol (meth)acrylate homo- and copolymers and the use of polymers thus prepared - Google Patents

Abstract

Processes for preparing polymers and copolymers by solution polymerization of monomers, where at least 0.01 mole per cent and up to 100 mole per cent of the monomers, based on the total polymerizable monomers, are alkoxypolyalkylene glycol (meth)acrylates of the following formula (I) in which R is hydrogen or methyl and R1 is an alkyl radical or an aryl radical having 1 to 50 carbon atoms, it being possible for R1 itself to be substituted by sulphur or nitrogen or by radicals containing sulphur or nitrogen, and in which n may represent a numerical value from 5 to 200 and m may represent a numerical value from 0 to 200, are characterized in that the solution polymerization is carried out continuously, using a mixing ratio of monomers and solvent that is outside the miscibility gap. The result is the possibility for economic preparation of copolymers having defined compositions in a relatively high concentration range relative to the solvent, without having to concentrate the solution of the polymer, or without the reaction being excessively exothermic.

Description

201114781 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing (meth)acrylic (alkoxy)polyalkanol ester homopolymers and copolymers and to the use of the resulting polymers. The invention more particularly relates to a continuous solution polymerization process in a suitable solvent, preferably water, from a homopolymer of (meth)acrylic acid methoxypropylene glycol ester, or with other monomers (e.g., preferably methyl methic acid) Providing a copolymer. [Prior Art] The solution polymerization method is an established method for preparing a polymer tailored from the production of a monomer. In particular, the further processing of these polymers may be preferably or only in a dissolved form, for example, as a film-forming resin. When it happens. In theory, from the point of view of process engineering, the solution polymerization method can perform the 'first borrowing' batch method (batch polymerization method) and the second borrowing continuous program in two variants. In addition, there are a wide variety of intervening variants that can be classified in the generic "half-batch" method. A known semi-batch process is referred to as "feeding process, wherein, during the polymerization reaction, at least one component, preferably one or more monomer components, is metered into the polymerization batch. In all cases the 'polymerization component must be in liquid form to be added to the polymerization reactor during a special period of time. In special cases, the 'monomer' has a specific by-product, which is a solid at room temperature. In bulk, or in the case of chemical or physical incompatibility, poor storage stability, or the presence of miscibility limits, the batch method requires two or more feed components (and the components must be accurately constructed with each other) ), so that the batch mixes quickly and has a efficiency of -5 - 201114781 (converted to a semi-batch method). Roughly, two fluids, usually a monomer composition and a chain transfer agent, in parallel, peroxidation The material (which is soluble in the solvent) is metered into the tank and thoroughly mixed, preferably at an elevated temperature (e.g., > 50 ° C), preferably in an inert gas, and polymerized for several hours. In particular, when used (meth)acrylic methoxy polymerization The diol (meth) acrylate (MPEG (meth) acrylate) as a monomer, the mutual solubility limit in the binary or ternary polymerization system occurs very often. Here, the "mutual solubility limit" more specifically refers to the specific concentration range, The components used in the polymerization can no longer be cleaved (i.e., uniformly) in the solvent. In this case, the solution becomes cloudy and the system separates, and the polymer formed afterwards no longer has a statistical composition, especially when When more than one monomer component is to be copolymerized. Depending on the position of the "inter-dissolution limit" in the mixture diagram, an important result of the mutual solubility limit is that it is impossible or impossible to produce the desired immobilized copolymer in an economical manner. The composition of the polymer. In fact, a common problem is that the monomer component can only be cleaved in a solvent at very low concentrations and no inevitable system separation is observed. A simple solution is The polymerization is carried out with a fairly highly diluted solution, but this is not only an economical point of view. If the monomer is introduced into the polymerization tank only at a relatively low concentration, the method The economy will be greatly limited. Therefore, the limitation of low supply concentration and mutual solubility limit means that only low concentration polymer solution can be obtained by batch method or semi-batch method, and the polymer content is in the best case. 25%, but often even the polymer content is only in the range of single digits. -6 - 201114781 When a higher concentration range is also used for the mixing of polymerization systems with solution polymerization with a fixed comonomer composition In the phenomenon, it is found that there is always or almost always a relatively high concentration of reactant regions in which the solution to be polymerized is homogeneous. Within these concentration ranges, the ratio is close to the overall polymerization reaction, provided that the monomers are compatible with each other. However, in the range of interest, the monomer concentration is often too high to make the proportional polymerization reaction practically impossible. First, it is impossible to remove the heat of polymerization that occurs, and, furthermore, the Trommsdorff effect leads to the polymer. Have unwanted and uncertain composition, or the polymerization is too early or completely stagnant. If it is desired to polymerize in a ternary system comprising the first monomer, comonomer and solvent in a predetermined monomer ratio over the average concentration range relative to the solvent, on the one hand the concentration of the reactants is brought to an economical state and the other In terms of achieving a reliable method state, such that there is no difficulty in removing the heat of polymerization, the contents of the reaction tank often pass through certain intermediate and higher concentration zones (often in the intermediate manufacturing phase) that are of great interest, in fact, When the mutual solubility limit occurs, as a result, a heterogeneous heterogeneous polymer inevitably occurs and as a result, the contents of the tank cannot be used. As already indicated above, in many applications it is possible to produce a polymer (for example, having a predetermined desired comonomer ratio) in a specially defined solvent at a predetermined concentration that is economically of interest, thereby allowing the polymer to It can be further processed, without additional separation steps, and it is very advantageous to directly process the solution in the same state. However, for the reasons mentioned, it is currently not possible. A method for the continuous solution polymerization of an acrylic monomer is substantially known from the person skilled in the art. Therefore, the basic principle of continuous polymerization of monomers is the subject of many publications. In particular, the following publications are cited in the context:

Ullmann's Encyclopedia of Industrial Chemistry, 1997 Vol A.21, keyword "Polymerization Processes", pp. 305-428

Hans-Georg Eliais Technologie 5th edition, 1992, pp. 10-114,119 EP 0 691 355 B1 W. Ring Zur kontinuierlichen Copolymerisation Makromolekulare Chemie 1964, 75, pp. 203-207 W. Ring Zur statistischen Copolymerisation Die Makromolekulare Chemie 101, 1967, Pp. 145-165 KH Reichert, H.-U. Moritz Polymer Reaction Engineering in Comprehensive Polymer Science ed. G. Allen, JC Bevington, Vol. 3, Chain Polymerization, Pergamon Press 1988, pp. 327-363

Polyacrylics from Synthetic Polymers: Technology, Properties, Application 1996, pp. 111-132

Macromers, pp. 573-574 from Concise Encyclopedia of Polymer Science and Engineering ed. Jacqueline I. Kroschwitz Wiley Interscience 1990 H. Gerrens Ober die Auswahl von Polymerisations reaktoren Chemie-lng. Tech. 52, 1980, pp. 477-488 US 4 546 160

Bero, Laczkowski und Pstrocki Investigations on the Continuous Copolymerization of Acrylnitrile with Methyl Methacrylate in a Heterogenous System, Vol. 2, 1964, pp. 5027-5074

Encyclopedia of polymer science and engineering John Wiley & Sons, Inc., Vol. 6, 1986, pp. 1-29

Adolf Echte Handbuch der technischen Polymerchemie, 1993, pp. 424-451, 558-559 The commonality of all of these publications is that they describe the continuous polymerization of monomers. However, none of these publications clearly indicates how the system can be used in situations where the monomer components to be polymerized cannot be mixed or cannot be completely mixed (this is economically interesting, ie, at an acceptable high concentration), and Suitable 8-8-201114781 For polymerization in a solvent that is further processed and does not require separation. SUMMARY OF THE INVENTION In view of the foregoing prior art and discussion herein, the present invention specifies a method that overcomes the shortcomings of prior art techniques associated with the polymerization of (meth)acrylic acid (alkoxy alcohol esters. In particular, The object of the present invention is to find ways to improve the supply method. Furthermore, the method of the invention can also reduce or completely overcome the problems, in particular they affect the problem of (meth)acrylic acid (alkoxy alkoxides. Furthermore, an improved space is proposed - A method of time yield, one of its purposes. By way of a method that has all the features of an independent patent application, it is not explicitly stated that these and other objects can be easily derived from the discussion in the introduction. Advantageous systems of the method of the invention The invention is protected by the patent application of the dependent application. [Embodiment] In particular, the fact that a method for producing a copolymer by solution polymerization of a monomer is used, wherein the total polymerizable monomer is % by mole and at most 1 00 mol% single system of the following formula (I) (the purpose of the alkoxy alkoxylated polyalkylene glycol ester) Miscible limit yl) polyalkoxy, although the present invention to achieve physical or derived polymers patents items 1 and at least 0.0 meth) acrylic -9 - 201114781 R CH3

II CH2 = C-(C0)-0-[CH2-CH20]n-[CH-CH20]m-Ri (|) wherein R is hydrogen or methyl and h is an alkyl group having 1 to 50 carbon atoms or The aryl group, I itself may be substituted by sulfur or nitrogen or a sulfur or nitrogen containing group, and wherein η may represent a number of from 5 to 200 and m may represent a number of from 0 to 200, characterized in that the solution polymerization is continuous By way of example, the mixing ratio of the monomer used and the solvent used is outside the mutual solubility limit, and the existing method can be modified in a manner not currently foreseen. In addition to the improvements described below, one of the advantages of the method of the present invention is the production of a homogeneous solution polymer which is initially immiscible or incompatible due to an excess of one or more components of the system: a) a monomer of formula (I), preferably MPEG ester / b) other monomers, such as methyl methacrylate (MAA) / and c) solvents, such as water, which were previously impossible or 'unable' because they could not be observed Or ignore the event state shown here, resulting in unwanted polymer composition and/or inhomogeneous sentence systems. Moreover, many other advantages can be realized in accordance with the present invention. These include, inter alia: - The individual reactant constituents in the self-reaction starting composition have a mixing ratio that is substantially fixed relative to each other. That is, during the polymerization reaction, the mixing ratio does not change or move, or there is no substantial change or movement. This alone allows the polymer composition to be uniform over a fairly narrow range of miscibility limits 10-201114781. - One of the results of a continuous situation is a reduction in security risks. Since the reaction zone is substantially smaller than the batch method and the instantaneous reduction in the amount of reactive species and increased space-time yield, virtually any uncontrolled reaction is excluded. - Accelerated reaction and improved control by substantially optimal introduction and/or removal of reaction energy. - Accelerate the reaction by increasing the temperature and/or pressure well above the boiling point of the solvent and driving the solvent out of the stagnant gas space. - Due to the closed tube and / or loop reactor system, it is not necessary to subject the tank to inert conditions, as in any previous batch method. - Use of the process of the invention to achieve high operational stability and / or high product quality. This stable state of the process of the present invention results in a consistent polymer composition. This is in contrast to the batch operation in which the quality of the product obtained varies from batch to batch. The method of the present invention is characterized in that the selected monomer-water mixture ratio is outside the range of mutual solubility limits. The "inter-dissolution limit" herein refers to a phenomenon in which the composition does not have a stable state at any ratio and at any temperature, that is, Possible state of unrealization. This phenomenon is observed in both liquid and solid. The mutual solubility limit is usually illustrated by the Τ-χ-phase diagram (binary mixture > mixed series) 'where three different substances can also form a triangle The composition itself is called the mixed phase. The mutual solubility limit is combined by two double junctions (temperature-dependent composition of the two phases). The double junction can be the intersection of low or high temperature. -11 - 201114781 and below) Critical point. The common node connects the equilibrium components of the two phases. In the binary system, these common nodes are always horizontal and therefore are usually not drawn in the diagram. The common nodes are used to define The composition thereof is two phases in the range in which the mutual solubility limit is disintegrated. The method for producing a polymer and a copolymer of the present invention relates to a (meth)acrylic acid (alkoxy) polyalkylene glycol ester of the formula (I). It R CH3 continuous solution polymerization

II CH2 = C-(C0)-0-[CH2-CH20]n-[CH-CH20]m-Ri (|) wherein R is hydrogen or methyl and R! is an alkyl group having 1 to 50 carbon atoms Or aryl, R" itself may be substituted by sulfur or nitrogen or a sulfur or nitrogen containing group, and wherein η may represent a number from 5 to 200 and m represents a number from 0 to 200. Suitable compounds of formula (I) include, for example, (meth) acrylates of alkoxylated aliphatic alcohols, such as alkoxylated butanol, while other alkoxylated alcohol starting materials are: methanol, ethanol, propanol, Pentanol (+ isomer), hexanol (+ isomer), cyclohexanol, methylcyclohexanol, 2-ethyl-hexanol and high-carbon aliphatic monohydric alcohols, such as isodecyl alcohol, iso-decyl alcohol Monool, isotridecyl alcohol, fatty alcohol made from natural raw materials. Also suitable for use as follows: based on alkoxylated phenols, for example, phenols, alkyl-substituted phenols (eg, tertiary butyl phenol, 2,6-xylenol), isomeric mixtures of technical grade alkanophenes ( Such as octylphenol, indophenol, dinonol, naphthol, alkyl-substituted naphthol), and also substituted alcohols (eg, decyl alcohol, tetrahydrofurfuryl alcohol, 2-methoxybutanol, 3- Methoxybutanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-methylamino-2-propanol, 3-methylamino-1-propanol, 2-tyrosolinylethanol , 2-(2-pyridyl)ethanol, 8 -12- 201114781 N-(2-ethyl) decyl D, N-(2-ethyl) oxime ratio 1, N-(2 - EOPO adduct of ethyl)pyrrolidone). It may also be, for example, an alcohol which represents a (statistical) adduct of ethylene oxide and propylene oxide with an alcohol such as butanol. The molar ratio of ethylene oxide and propylene oxide units in monomer component I can be between 96:4 and 6:94. As an indicator of the molecular weight of the preferred monomer of formula (I), this range may be about 2,000 otocepts. However, this does not constitute any limitation. Depending on the degree of alkoxylation (n + m, formula I) and depending on the size of the group R, higher molecular weights can also be achieved, up to about 5,000 oar. The monomer of formula (I) may itself be present in the form of a mixture of the methacrylates of the different alkoxylated alcohols described above. If the R in the polymerized compound of formula (I) is a methyl group, particular interest is given to the process of the invention. These are more particularly monomers of the alkoxy (polyalkanol) methacrylate type. A further preferred method is characterized in that Ri in the polymerized compound of formula (I) is an alkyl group having from 1 to 50 carbon atoms, advantageously from 1 to 20 carbon atoms. Particularly preferred R! is a linear or branched alkyl group having 1 to 8 carbon atoms. More preferably, the I group in the formula (I) is selected from the group consisting of an alkyl group of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. In the present invention, it is particularly advantageous that 1 is (^3. In the latter case, the compound of the formula (1) is a monomer of the (meth)acrylic acid methoxy (polyalkylene glycol) ester type. According to the present invention, it is particularly advantageous. The method uses a compound of the formula (I) wherein R and R1 are both methyl. These are methoxy (polyalkylene glycol) methacrylates. The superscripts η and m in the formula (I) are used to determine The number of repeats of the alkanediol unit (more specifically -13-201114781 is the ethylene glycol and propylene glycol unit). The monomer of formula (1) has 5 to 200 repeating units derived from ethylene glycol and 〇 to 200 A repeating unit derived from propylene glycol. In an advantageous system of the invention, the number ' of the subscript η is in the range of 5 to 100, more preferably 5 to 50, still more preferably in the range of 5 to 30, and still more Preferably, it is in the range of from 7 to 25. More advantageously, in a preferred modification of the method of the invention, the number 下 of the subscript η is in the range of 〇 to 100, more preferably 50, more preferably 0 to 10. In the range of 〇 to 5, it is particularly advantageous that the subscript m is 0. In the latter case, only one of the monomers of the formula (I) is derived from A repeating unit of polyethylene glycol. In this case, the compound of formula (I) is an alkoxy (polyethylene glycol) ester of (meth)acrylic acid. The monomer of formula (I) comprises both ethylene glycol and propylene glycol. When the repeating unit (m is not equal to 0), the repeating units may be distributed in a statistical manner (which is random in order) in the monomer of the formula (I), or in the block. Preferably, they are arranged in a block manner. It is also possible to have multiple blocks present, so one polyethylene glycol block is followed by a polypropylene glycol block followed by a polyethylene glycol block, etc. In a particularly preferred system, the monomer of formula (I) is Poly(ethylene) (meth)acrylate (PEG (meth)acrylate), methoxypolyethylene glycol (meth)acrylate (MPEG (meth)acrylate) or (meth)acrylic acid polypropylene glycol Ester (PPG (meth) acrylate). Particularly preferred is (meth) glyceric acid polyethylene glycol vinegar or (meth) propyl methic acid methoxy-14 - 201114781 based polyethylene glycol ester. In the method, one compound of the formula (I) may be polymerized, but two or more kinds may be polymerized. The same compound of the formula (I). Preferred is a mixture of polyethylene glycol (meth)acrylate and methoxypolyethylene glycol (meth)acrylate, or (meth)acrylic acid having a molecular weight MW different from each other. a mixture of polyethylene glycol esters or a mixture of methoxypolyethylene glycol (meth)acrylates having a molecular weight MW different from each other. The molecular weight MW of the (alkyl)polyalkylene glycol ester is substantially 2000 to 20, The gram/mole ' is preferably 3000 to 1 Torr, gram/mole, more preferably 4,000 to 6,000 g/mole. The molecular weight in the present invention means the weight average MW of the molecular weight. The process of the invention 'in addition to a homopolymer of a monomer of formula (I) or a copolymer having two or more different monomers of formula (1), it is also possible, and preferably, to produce a monomer other than formula (I) In addition, copolymers containing monomers other than the other are included. Essentially, in an advantageous modification, the invention is carried out such that a) is 0.01-99.99 mol/. The alkoxy polyalkylene glycol (meth)acrylate of the above formula is copolymerized with b) 99·99-〇.〇1 mole or a plurality of ethylenically unsaturated monomers copolymerizable with a), a) and b) A total of 1 〇〇 mol % polymerizable component was added. The ethylenically unsaturated monomer capable of copolymerizing with a) means those monomers different from a) and conforming to the following formula (Ila) -15 - 201114781

Wherein 11 and 112 are each independently selected from the group consisting of hydrogen, halogen, CN, and a linear or branched alkyl group having 1 to 20 (preferably 1 to 6, particularly preferably 1 to 4) carbon atoms (which may be 1) Substituted to (2n+l) halogen atoms, wherein η is the number of carbon atoms of the alkyl group (e.g., CF3)), α having 2 to 10 (preferably 2 to 6, more preferably 2 to 4) carbon atoms, /3-unsaturated linear or branched alkenyl or alkynyl group (which may be substituted by 1 to 2 2 -1 ) halogen atoms (preferably chlorine), wherein η is the number of carbon atoms in the alkyl group) (for example, CH2 = CC1-), a cycloalkyl group having 3 to 8 carbon atoms which may be substituted by 1 to (2n-1) halogen atoms (preferably, chlorine), wherein η is the number of carbon atoms of the cycloalkyl group) An aryl group having 6 to 24 carbon atoms which may be substituted by 1 to (2η-1) halogen atoms (preferably chlorine) and/or an alkyl group having 1 to 6 carbon atoms, wherein η is an aryl group Number of carbon atoms; C(=Y>) R5·, C (=Y*) NR6*R7·, Y*C (=Υ·) R5*, SOR5*, S02R5*, oso2R5*, NR8*S〇2R5 ·, PR5,, P (=Υ·) R5%, Υ·ΡΚ·"2, Y*p (=Y*) R"2, NR8, which are added via additional R", aryl or heterocyclic groups Level four Wherein Y* may be NR", S or Ο'O is preferred; R5# is a fluorenyl group having 1 to 20 carbon atoms, a thiol group having 1 to 20 carbon atoms, and 〇Rl5 (R15 is hydrogen or An alkali metal), an alkoxy group having 1 to 20 carbon atoms, an aryloxy group or a heterocyclic oxy group; the ruthenium and the ruthenium are independently hydrogen or an alkyl group having 1 to 2 carbon atoms, or a combination thereof An alkylene group having 2 to 7 (preferably 2 to 5) carbon atoms, in each case, they form a 3- to 8-membered ring, preferably a 3- to 6-membered ring, and a ruler 8 is hydrogen or a linear or branched alkane having from 1 to 20 carbon atoms 8 -16-201114781 or an aryl group; wherein R4# is independently selected from the group consisting of hydrogen, halogen (preferably fluorine or chlorine), and an alkane having 6 carbon atoms And COOR9t, wherein R" is hydrogen, an alkali metal or an alkyl group having from 1 to 40 carbon atoms, or a ruler" and a ruler" can be converted into a group of the formula (CH2) 'J η *, which can be passed through 1 to 2η'halogen atom or a group substituted with (^ to C4 alkyl group, or a formula C(=0)-Y*-C(=0), wherein η' is 2 to 6, 3 or 4 is preferred, Υ* as defined in the specification; and at least two of the groups RM, R2·, 11〃 and 114# are hydrogen or halogen These monomers include, inter alia: aryl (meth)acrylates, such as benzyl methacrylate or phenyl methacrylate, wherein the aryl groups are each unsubstituted or substituted to a higher degree; methacrylates of halogenated alcohols Such as 2,3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, 2-bromoethyl methacrylate, methacrylic acid 2-iodoethyl ester, chloromethyl methacrylate; vinyl halide such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; vinyl ester such as vinyl acetate; styrene, side chain with alkyl substitution Substituted styrenes (such as α-methylstyrene and α-ethylstyrene), substituted styrenes having an alkyl substituent on the ring (such as vinyl toluene and p-methylstyrene) And halogenated styrene (such as monochlorostyrene, dichlorostyrene, tribromostyrene and tetra-17-201114781 bromostyrene); heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine , 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5 Alkenylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylribromazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole , N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidone, 3-vinylpyrrolidone, N-vinylcaprolactam, N-Ethylbutene decylamine Tetrahydrofuran (vinyloxolane), vinylfuran, vinylthiophene, vinylthiazine, vinylthiazole and hydrogenated vinylthiazole, vinyloxazole and hydrogenated vinyloxazole; vinyl ether and isoprene a maleic acid; a maleic acid and a maleic acid derivative such as maleic anhydride, methyl maleic anhydride, maleimide, and methyl maleimide; a fumaric acid and a fumaric acid derivative; acrylic acid and methacrylic acid; a diene such as divinylbenzene. a hydroxyalkyl (meth) acrylate such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ( 2,5-dimethyl-1,6-hexanediol methyl methacrylate, 1,1 〇 癸 癸 glycol ester of (meth) acrylate; methacrylate containing carbonyl group, such as 8 -18- 201114781 2-carboxyethyl methacrylate, carboxymethyl methacrylate, oxazolidinyl methacrylate, N-(methacryloxy)carbamamine, acetone methacrylate, N-methyl Propylene decylmorpholine, N-methylpropenyl-2-pyrrolidone, N-(2-methylpropenyloxyethyl)-2-pyrrolidone, N-(3-methylpropenyloxyethyl) -2-pyrrolidone, N-(2-methylpropenyl phthalate pentadecyl)-2-pyrrolidone, N-(3-methylpropenyloxyhexadecyl)-2-pyrrolidone: Aminoalkyl methacrylate and amine alkyl (meth) acrylamide, such as N-(3-dimethylaminopropyl)methacrylamide, dimethylaminopropyl methacrylate, methyl 3-diethylammonium acrylate, (meth)acrylic acid 3- Butyl hexadecane; nitrile of (meth)acrylic acid and other nitrogen-containing methacrylates such as N-(methacryloxyethyl)diisobutyl ketone imine, N-(A Propylene methoxyethyl) bis(hexadecyl) ketimine, methacryl fluorenyl amide acetonitrile, 2-methyl propylene methoxyethyl methyl cyanamide, cyano cyanoacrylate Ester; a heterocyclic (meth) acrylate such as 2-(1-imidazolyl)ethyl (meth)acrylate, -19-201114781 2-(4-morpholinyl)ethyl (meth)acrylate and 1-(2-Methylacrylic acid ethyl)-2-indolopyranone: epoxy methacrylate such as 2,3-epoxybutyl methacrylate, methacrylic acid 3, 4-epoxybutyl butyl ester, 10,11-epoxy undecyl methacrylate, 2,3-epoxycyclohexyl methacrylate, 10,11-epoxy hexadecane methacrylate Ester; and glycidyl methacrylate. Particularly suitable comonomers b) include, in particular, methacrylates, acrylates, styrene and mixtures comprising two or more of the foregoing groups. Examples of (meth) acrylates are methyl methacrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. Ester, isobutyl (meth)acrylate, hexyl (meth)acrylate, ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (A) Base) isodecyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenethyl (meth) acrylate, 3,3,5-trimethylcyclohexane (meth) acrylate Ester, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, methyl- or ethyl-triethylene glycol methacrylate, butyl diglycol methyl methacrylate, di(methyl) Ethylene glycol acrylate and diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and their high carbon homologues, dipropylene glycol di(meth)acrylate, di(a) Base) propionic acid dipropanol vinegar and their high carbon homologs, di(methyl)propionic acid 8 -20- 201114781 1,3- 1,4-butanediol ester, 1,6·hexanediol di(meth)acrylate, 1,1 2-dodecanediol di(meth)acrylate, glycerol di(meth)acrylate , trimethylolpropane tris(meth)acrylate, trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane and tris(methyl) of 3-10 mol ethylene oxide Acrylate, ethoxylated bisphenol-oxime with 2-20 moles of ethylene oxide (preferably 2-10 moles of ethylene oxide) of di(meth)acrylate and/or having 1-15 epoxy Polyethylene glycol dimethacrylate and allyl (meth)acrylate of the alkane unit. Further examples are monoesters of (meth)acrylic acid, (meth)acrylamide, N-methylol (meth)acrylamide, maleic acid and succinic acid with hydroxyethyl methacrylate, And phosphates of hydroxyethyl (meth)acrylate (the ratio is usually not high). Furthermore, it will be appreciated that variants of two or more monomers b) can also be used to make the polymer. Thus, the polymer can also be obtained by polymerizing a variant a) with two or more variants of two or more a) having two or more different monomer variants b). A particular variant of the process according to the invention is characterized in that as component b) the copolymerizer is one or more copolymerizable compounds R of the formula (II),

I CH2 = C-(C0)-0-R2 (II) wherein R' is hydrogen or methyl and R2 is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms or having 4 to 32 carbons A cycloalkyl group of an atom. Here, the linear or branched alkyl group having 1 to 20 carbon atoms is preferably an unbranched or branched hydrocarbon group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl or isopropyl. , 1-butyl, 2-butyl, 2-methylpropyl or tertiary butyl-21 - 201114781; and, for example, pentyl, 2-methylbutyl, 1,1-dimethylpropyl , hexyl, heptyl, octyl or 1,1,3,3-tetramethylbutyl; and, for example, 'indenyl, 1-indenyl, 2-indenyl, eleven, twelve, fifteen a cycloalkyl group having 4 to 32 carbon atoms means a cyclic fluorenyl group having 4 to 32 carbon atoms, preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, Cycloheptyl or cyclooctyl. A particularly advantageous modification of the process of the invention is characterized by the copolymerization of the compound of formula (II) wherein R' is methyl, as component b). In another preferred modification of this method, in the procedure employed, the copolymerized component b) is a compound of formula (II) wherein R 2 is hydrogen. In a highly advantageous system of this process, the monomer b) used is (meth)acrylic acid, preferably methacrylic acid (MAA). Here, in the present invention as a whole, the (methyl) brackets represent the alternate use of two specified substances' or their combined use. For example, (meth)acrylic acid represents the use of methacrylic acid or a mixture of methacrylic acid and acrylic acid. The object of the process of the present invention is to produce a copolymer having a broad range of monomer ratios (expressed in mole percent) for making the copolymer. In a preferred variation of the method, component a) is copolymerized in an amount of from 1 90 to 90 mol% and component b) is copolymerized in an amount of from 90 to 10 mol%, a) and b) plus a total of 1 〇〇 Moor. /. Polymerizable components. A more preferred variant of this process comprises the combination of component a) copolymerization in an amount of from 3 to 7 mol%, and component b) in an amount of from 70 to 30 mol%, a) and 1)) plus total 1 〇〇 mole % polymerizable component. -22- 201114781 It is also advantageous that 'component a) is copolymerized in an amount of 40 to 90 mol% (preferably 55 to 9 mol%) and component b) is 60 to 1 mol% (preferably) 4 5 to 丨〇mol %) amount of copolymerization, a) and b) plus a total of 100 m. /〇. Monomer a) and optionally b) are polymerized in solution. The solvent used herein is a reagent known to those skilled in the art. Therefore, in the preferred modification of this method, the polymerization or copolymerization reaction can be carried out in an organic solvent. Particularly suitable organic solvents are alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, higher alcohols (ethylene glycol, glycerol), polyether polyols (polyethylene glycol) and ethers. Alcohols (such as butanediol, methoxypropanol and alkyl polyethylene glycols) but can also be aldehydes, esters, ethers, decylamines or ketones (especially acetone, methyl ethyl ketone), hydrocarbons (especially Methyl ester, ethyl ester, isopropyl ester, heptane, cyclohexane, xylene, toluene, petroleum solvent and mixtures thereof). Preferred for these considerations are ethyl acetate, ethanol, isopropanol or heptane, and mixtures thereof. Particularly preferably, water acts as an additional additive. Further preferred is a mixture of water and alcohol in an amount of more than 50% by weight, preferably more than 5% by weight, particularly more than 80% by weight, based on the total weight of water and organic solvent. More preferably, water is used completely as a solvent. The solution polymerization of monomer a) and optionally b) is preferably carried out by radicals. For this purpose, an initiator is used. Conventional free radical polymerization reactions are fully described in the literature, including UUmann's Encyclopedia o f I n d u s t r i a 1 C h e m i s t r y, S i x t h E d i t i o n 〇 In the present invention, the polymerization reaction is initiated using at least one polymerization initiator for radical polymerization. This initiator includes, inter alia, the azo initiators known in the art from -23 to 201114781 (eg 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-di) Methylvaleronitrile) and 1,1-azobiscyclohexanecarbonitrile, organic peroxides (such as bisisophenylpropyl peroxide), dithiol peroxides (such as dilaurin peroxide), Peroxydicarbonate (such as diisopropyl peroxydicarbonate), perester (such as peroxy-2-ethylhexanoic acid tertiary butyl vinegar), etc. are used for the purpose of the present invention. Suitable polymerization initiators include, inter alia, the following compounds: methyl ethyl ketone peroxide, acetoxyphenone, dilaurin peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, Tert-butyl octanoate, methyl isobutyl ketone, cyclohexanone peroxide, dibenzyl hydrazine peroxide, tertiary butyl peroxybenzoate, tertiary butyl peroxy isopropyl carbonate, 2 , 5-bis(2-ethylhexylperoxy)-2,5-dimethylhexyl, peroxy 2-ethylhexanoate tert-butyl ester, peroxy 3,5,5- Tertiary butyl trimethylhexanoate, bisisophenylene peroxide 1,1-bis(tri-butylperoxy)cyclohexane, -24 - 201114781 1,1-bis(tertiarybutylperoxy)-3,3,5-trimethylcyclohexane Isopropyl propyl hydrogen peroxide, tertiary butyl hydroperoxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, 2,2'-azobisisobutyronitrile, 2,2 '-Azobis(2,4-dimethylvaleronitrile), 1,1-azobiscyclohexanecarbonitrile, diisopropyl peroxydicarbonate, tertiary amyl peroxyisobutyrate, Di-(2,4-dichlorobenzylhydrazine) peroxide, tertiary butyl peroxy tertiary valerate, 2,2'-azobis(2-amidinopropane) dihydrogen chloride, peroxide II 3,5,5-trimethylhexyl), dioctyl peroxide, dinonyl peroxide, 2,2'-azobis-(N,N'-dimethylammonium) , bis-(2-methylbenzylhydrazine) peroxide, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(2-methylbutyronitrile), 2,5-Dimethyl-2,5-bis(2-ethylhexylperoxy)hexane 4,4'-azobis(cyanovaleric acid), di-peroxide-(4- Methyl benzamidine), dibenzyl hydrazine peroxide, peroxygen Amyl 2-ethylhexanoate three vinegar, -25-201114781 three-butyl peroxy-2-ethylhexanoate, three-butyl peroxy isobutyrate the polymerization mixture and the initiator agent. The polymerization used to make the polymers and copolymers can be carried out in the presence or absence of a chain transfer agent. Preferably, the polymerization is carried out in the presence of a chain transfer agent. Chain transfer agents which can be used include the typical species described in the free radical polymerization. Mercaptans are particularly recommended, for example, n-butyl mercaptan, n-dodecyl mercaptan, 2-mercaptoethanol, indole acetic acid and its homologous compounds, 2-ethylhexyl acetate or pentaerythritol tetraacetate; chain transfer The amount of the agent is preferably from 0.05% by weight to 5% by weight. More preferably, the amount is 〇. /. To 2.0% by weight and an excellent amount is 0.2% by weight to 1.% by weight, based on the total mass of the ethylenically unsaturated compound (component a) and b). In this regard, those skilled in the art can refer to the technical literature, in particular H. Rausch-Puntigam, T. V δ 1 k e r , "A c r y ί - und Methacrylverbindungen", Springer,

Heidelberg, 1 967 ; Houben-Weyl “Methoden der organis chen Chemie,, vol. XIV/1, p.66ff, Georg Thieme, Heidelberg, 1961 and Kirk-Othmer, “Encyclopedia of

Chemical Technology,,, Vol. 1, pages 296ff, J. Wiley, New Y o r k, 1 9 7 8. In the present invention, a water-soluble chain transfer agent such as indole acetic acid and its homologous compound is particularly preferred. In a preferred system, they are used in an amount of from 5% by weight to 5% by weight based on the total mass of the compounds a) and b). According to the invention, it is used in the copolymerization of (meth)acrylic alkoxypolyalkylene glycol 8 -26- 201114781 (preferably (meth)acrylic acid methoxypolyethylene glycol ester or preferably with methacrylic acid) Solution polymerization in a suitable dissolved 'water', the individual components are co-currently separated, for example, the monomer mixture and the chain transfer agent and the dissolution include a high concentration), which is metered through the mixer to the existing tube or circulation. In the reactor, this metering is introduced into the desired output and the residence/reaction time without bubbles, and the tube or ring is selected. When desired, in a specific modification of the invention, or in addition to a particular method of the invention, (A) forming at least one of the monomers comprising at least one of the formula (D) can be initiated in the monomer stream (A) The initiator stream of the polymerization initiator; (B) the fluid from (A) is polymerized in the reaction zone at -20 ° C: range; and (C) the polymer stream is discharged from the reaction zone. Monomer stream and initiator stream, other fluids (such as chain transfer agent streams). The monomer stream comprises monomers of (I). Among the advantageous modifications of the method, the monomer species (Π) or (Ila) (preferably) For the negative of formula (II), many factors determine the formula (I) monomer and formula (II). As the artisan considers, these factors include the physical properties of 5, the choice of monomer of formula (II), And the nature of the poly. However, in the present invention, the ratio is mainly determined by the mutual solubility in different selected solvents. Preferably, the homopolymer (e.g., preferably, or advantageously) Oxide (performed at the reaction temperature. According to the diameter and long component of the stream), body flow, and inclusion The temperature of the monomer free radical g 1 50 t and, if necessary, at least one of the formulae comprises at least one monomer. The ratio of the monomers, the oxime (I) monomer complex and the copolymer monomer The beneficial significance is in -27-201114781 to understand the binary (preferably ternary) system, and the presence or absence of the mutual solubility limit of the system consisting of monomer I, monomer π and solvent. Usually, the components are selected. And when the application amount is selected, the mutual solubility of the monomers to be put together for the reaction and the polymerization reaction in the solvent will be investigated. Here, the ratio of the comonomer 1: comonomer 2 is 80: 2 〇 In the example of the Mox % composition, the goal is to obtain an aqueous dispersion having a solids content of 50%, the selected concentration (where 80: 20 monomer mixture is present at different concentrations in the water with a mutual solubility limit) will be monomer and water The mutual solubility exists and the concentration of the solid content is 50% or higher. The continuous copolymerization reaction is carried out to remove the heat of reaction without problems, and at the same time, achieve a high solid content; if necessary, after the end of the polymerization reaction, Diluted by further solvent, dissolved Adjust to target concentration. For solution polymerization, at least one of the fluids used contains a solvent. If necessary, the monomer stream contains a solvent. Use this type of solvent as previously specified to dissolve the monomer to aid The heat transfer in the polymerization reaction, or the viscosity of the target product is lowered. As mentioned earlier, preferably, the solvent is selected from the group consisting of water, alcohols, ethers, esters, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated A mixture of these and the choice of the type and amount of solvent is determined by the polymerization conditions (including the reaction temperature). Water and alcohol (such as methanol, ethanol and isopropanol) are preferred. The initiator stream contains Free radical initiator. Likewise, as already mentioned earlier, the initiator is preferably selected from the group consisting of persulphates, hydrogen peroxide, organic peroxides and hydroperoxides, azo compounds and redox initiation. (such as hydrogen peroxide plus iron ions). Preferred are persulphates such as ammonium persulfate and potassium. -28- 201114781 When desired, the initiator stream contains a solvent. A solvent is used to dissolve or dilute the initiator to control the rate of polymerization or to aid in heat transfer or mass transfer of the polymerization. Suitable solvents are described above. The choice of solvent type and amount will depend on the nature of the initiator and the polymerization conditions. When a persulfate initiator is used, water and an alcohol such as methanol, ethanol and isopropanol are preferred. When desired, the monomer stream and initiator stream comprise a chain transfer agent. Suitable chain transfer agents include the compounds previously described. Also advantageous are alkylamines, alkyl sulfides, alkyl disulfides, carbon tetrachloride, allyl ethers and mercaptans. Thiols such as butanol, indole acetic acid and decanoic acid are preferred. Under certain conditions, it is preferred to add the chain transfer agent (if used) in a separate stream. If the chain transfer agent is mixed with an initiator or a monomer to cause decomposition of the initiator or polymerization of the monomer, it is particularly desirable to add the chain transfer agent as a separate stream. This is especially important on a large industrial scale, as these reactions can cause safety problems. When desired, the fluid having the chain transfer agent comprises a solvent which is used to dissolve or dilute the chain transfer agent. Suitable solvents include water, alcohols, ethers, esters, ketones, aliphatic and aromatic hydrocarbons, halides, and the like, and mixtures thereof. The choice of type and amount of solvent is determined by the nature of the chain transfer agent and the polymerization conditions. Preferred are water and alcohols (e.g., methanol, ethanol, and isopropanol). The monomer stream, the initiator stream, and, if used, the chain transfer agent stream is polymerized in the reaction zone. The reaction temperature preferably remains substantially stable during the polymerization. This temperature is determined by a combination of factors including the molecular weight of the polymer product to be combed, the type and concentration of the initiator, the type and concentration of the monomer, and the solvent used. The reaction is carried out at a temperature in the range of -2 0 to 150 °C, preferably -29-201114781 in the range of 0 to 100 °C. 20 to 90 ° C is better. The optimum range is 40 to 60 °C. The rate of addition of each fluid depends on the desired concentration of each component, the size and shape of the reaction zone, the reaction temperature, and many other considerations. Generally, the fluid flows into the reaction zone at a rate such that the initiator concentration is maintained in the range of 0.01% by weight to 1% by weight and the chain transfer agent concentration is maintained in the range of 0.1% by weight to 1.5% by weight. The polymerization occurs in the reaction zone. This zone may have the form of a tank reactor, a tube reactor, a loop reactor or any other desired reactor. The reaction zone is preferably equipped with a mixer, a heat exchange unit, a source of inert gas, and any other suitable means for discharging the polymer stream during the polymerization of the reaction zone. The flow rate of the polymer stream allows the material balance to outweigh the conditions in the reaction zone. This means that the amount of material flowing into the reactant corresponds to the amount of material discharged from the reaction zone. The polymer stream is then collected. Advantageous modifications of the process of the invention include in step (A) - forming an additional chain transfer agent stream, or - the monomer stream comprises a chain transfer agent, or - the initiator stream comprises a chain transfer agent; or - said Two or three of the application variants of the chain transfer agent are used in combination. In a preferred process variant, the fluid is directed to the reaction zone of the tube or loop reactor and reacted, optionally before mixing in the mixing zone. Hereinafter, the present invention will be described in more detail with reference to working examples and comparative examples, and with reference to the accompanying drawings. -30- 201114781 Procedure for determining the mutual solubility limit of MPEG2000 ΜΑ / MAA / water system To obtain a triangular diagram illustrating the range of immiscible concentrations of the aforementioned systems, individual concentration blends were made in the following manner. In a 125 ml wide-necked glass vial, individual components are weighed in an appropriate mass ratio, such as 5 grams of PLEX 6934-0 (MPEG 2000® > 50% in water), 5 grams of MAA, and 90 grams of water; when PLEX 6934 The water ratio of -0, 2.5 g, was added to water weighing 90 g to obtain an absolute composition of 2.5 g of MPEG 2000 MA, 5 g of MMA and 92.5 g of water (water = completely demineralized water). After the batch was mixed in a controlled climatic environment at 23 ° C, a clear homogeneous solution was obtained. In this figure, black dots are marked here. Then, the solution was heated to 50 ° C in a water bath or in a forced air drying oven for 4 hours, then shaken and visually evaluated under a light source. A clarified homogeneous solution is also obtained here: in the 5 ° ° C diagram, the black solid point is marked. Thereafter, the sample was heated to 80 ° C, also in a water bath or dry box for 4 hours, then shaken and re-evaluated. At 80 °C, the sample is now clearly separated, resulting in a turbid emulsion; in the 8 〇 °C plot, at the intersection of this composition, a hollow spot is marked. To complete this figure, use a similar procedure at different temperatures using all mixing ratios under test. In the range of 0-10% MAA, for example, MPEG 2000 ΜΑ > M A Α content is studied in terms of 1% pitch, specifying the effect of temperature on the mutual solubility of components within this limit. Accordingly, it is expected that further increase in temperature will further move to immiscible. Since the MPEG used is the 5 〇% strength solution -31 - 201114781 liquid in its supply form, the reverse calculation from the supplier table is performed 'in the figure' based on their pure MPEG-MA content content' MPEG methacrylates in pure form and in various blends are clearly indicated. The results provide a comprehensive overview of the mutual solubility limits present and clearly show the range of immiscibility. In this case, a 5% or 10% mixture pitch is selected in each case. For more accurate results, the monomer amount can be changed in 1% steps. Since then, the transition from homogeneous to heterogeneous mixtures has been evident and the critical GMAA (=methacrylic acid) concentration and high temperature dependence are very accurate. For example, a mixture of MPEG2000 / 7_K / GMAA = 05/90/05 is uniform at 5〇t (please refer to the corresponding point in the figure, solid and round). At 80 ° C, the mixture became uneven (please refer to the corresponding points in the figure, round, hollow). [Simple diagram of the diagram] Figure 1 is a ternary mixture of MPEG-750-MA / methacrylate / water 50% strength aqueous solution at 23 ° C (Figure la), 50 ° C (Figure lb) and 80 ° C (Fig. lc) phase diagram, which has been standardized for pure MPEG-750 methacrylic acid vinegar; Figure 2 is a three-dimensional strength solution of ^-〇-2000-\1 八/methacrylate/water The mixture was normalized at 23 ° C (Fig. 2a), 5 (TC (Fig. 2b) and 80 °C (Fig. 2 ,, this figure has been standardized for pure MPEG-2000 methyl acrylate vinegar; Figure 3 MPEG-5000-MA / methacrylate / water 5% strength - 32 - 201114781 A ternary mixture of aqueous solutions at 23 ° C (Figure 3a), 50 °C (Figure 3b) and 80 °C (Figure 3c) Phase diagram, this figure has been standardized for pure MPEG-5000 methacrylate. In the figure: • Representative composition has clear mutual solubility (homogeneous, miscible component ratio, outside the mutual solubility limit) 〇 represents composition lacking mutual solubility (Inhomogeneous, immiscible component ratio, within the mutual solubility limit) -33-

Claims (1)

201114781 VII. Patent Application Range: 1. A method for producing polymers and copolymers by solution polymerization of monomers, wherein the total polymerizable monomer is at least 0.01 mol% and at most 100 mol% of the single system. Alkoxypolyalkylene glycol (meth)acrylate of formula (I) R CH3 II CH2 = C-(CO)-0-[CH2-CH2〇3n-[CH-CH2〇]m-Ri (I) Wherein R is hydrogen or methyl and Rt is an alkyl or aryl group having 1 to 50 carbon atoms; I itself may be substituted by sulfur or nitrogen or a sulfur or nitrogen-containing group, and wherein η may represent from 5 to 200 The number 値 and m may represent a number of 〇 to 200, characterized in that the solution polymerization is carried out in a continuous manner, and the mixing ratio of the monomer used and the solvent is outside the miscibility gap. 2. The method of claim 1, wherein in the compound of the formula (I), R is a methyl group. 3. The method of claim 1 or 2, wherein the compound of the formula (I) is polymerized. , 1^ is a methyl group. 4. The method of claim 1 or 2, wherein in the compound of the formula (I) polymerized, m is hydrazine. 5. The method of claim 1 or 2, wherein a) 〇·01·99·99 mol% of the (meth)decenoic acid decyloxypolyalkylene glycol of the above formula (I) and b 99.99_〇.〇1 mole % - or a plurality of ethylenically unsaturated monomers copolymerizable with a), 8 201114781 a) and b) plus a total of 100 mole %. 6. The method of claim 5, wherein the polymerizable compound of the formula b) or the plurality of formula (II) is copolymerized, R, I CH2 = C-(C0)-0-R2 (II) wherein R 'It is hydrogen or methyl and R2 is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 32 carbon atoms. 7. The method of claim 6, wherein R' in the compound of formula (II) copolymerized as component b) is a methyl group. 8. The method of claim 6, wherein r2 in the compound of formula (II) copolymerized as component b) is hydrogen. 9. The method of claim 5, wherein the copolymerization amount of component a) is 10 to 90 mol% and the copolymerization amount of component b) is 90 to 10 mol%, 〇 and b) plus a total of 100 Moer%. 10. The method of claim 8, wherein water is used as a solvent for solution polymerization. 11. The method of claim 1 or 2, wherein (A) forming a monomer stream comprising at least one monomer of formula (I), and comprising at least one capable of inducing presence in monomer stream (A) An initiator stream of the initiator of the radical polymerization of the monomer; (B) the fluid from (A) is polymerized in the reaction zone at a temperature ranging from -20 ° C to 150 ° C; and (C) is discharged from the reaction zone Polymer flow. 12. The method of claim 11, wherein the polymerization reaction is carried out at a temperature ranging from 20 ° C to 90 ° C. 13. The method of claim 11, wherein the polymerization occurs in a temperature range of from 40 °C to 60 °C. 14. The method of claim 11, wherein in step (A) - forming an additional chain transfer agent stream, or - the monomer stream comprises a chain transfer agent, or - the initiator stream comprises a chain transfer agent; Or a combination of two or three of the above-described application variants of the chain transfer agent. The method of claim 11, wherein the monomer stream formed and polymerized in step (a) comprises a solvent, preferably For water. The method of claim 11, wherein the initiator stream formed and polymerized in step (a) comprises a solvent. The method of claim 11, wherein the fluid is introduced into the reaction zone in the tube reactor or the loop reactor and reacted, as the case may be, the fluid is previously mixed in the mixing zone. -36-