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    POLYMER DISPERSION, PROCESS FOR THE PREPARATION OF POLYMER DISPERSIONS, AND, USE OF POLYMER DISPERSION A finely divided polymer dispersion containing starch that can be obtained by emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one initiator of ethylenically unsaturated redox and starch, where (a) from 0 to less than 40% by weight of at least one optionally substituted styrene, (b) from more than 60 to 100% by weight of at least one C1-C12- acrylate alkyl and / or a C1-C12-alkyl methacrylate, (c) from 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer, are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% and based on the active monomer content and (d) from 15 to 40% by weight of at least one degraded starch that has a Mw molar mass from 1000 to 65,000 g / mol, with based on the total weight of the solids content of the components (a) + (b) + (c), are used with o starch and polymerization being carried out in the presence of at least 0.01% by weight, based on the monomers used, at least one chain transfer agent containing terpene and in which (...).
    公开号:BR112014008717B1
    申请号:R112014008717-2
    申请日:2012-10-11
    公开日:2021-02-02
    发明作者:Carmen-Elena Cimpeanu；Holger Kern；Petra Arnold；Christoph Hamers
    申请人:Basf Se；
    IPC主号:
    专利说明:

    [01] The invention relates to finely divided polymer dispersions, containing starch, which can be obtained by emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one redox initiator, starch and chain transfer agent, processes for the preparation of dispersions and their use as sizing agents and coating materials for papers.
    [02] EP 0 273 770 B1 and EP 0 257 412 B2 describe sizing agents based on finely divided aqueous dispersions that can be obtained by copolymerizing ethylenically unsaturated monomers, such as acrylonitrile and (meth) acrylates and optionally up to 10 % by weight of other monomers, such as styrene, by emulsion polymerization in the presence of initiators comprising peroxide groups, in particular redox initiators and degraded starch. The use of chain transfer agents, such as terpenes, is not described in any of the documents.
    [03] WO 99/42490 A1 likewise describes aqueous finely divided polymer dispersions that are used for sizing the surface of paper, cardboard and cardboard. The dispersions can be obtained free radical polymerization in emulsion of ethylenically unsaturated monomers in the presence of degraded starch that has an average molecular weight in number Mn from .500 to 10,000. The monomers consist of (i) at least one optionally substituted styrene , (ii) at least one C1-C4-alkyl (meth) acrylate and (iii) optionally up to 10% by weight of other ethylenically unsaturated monomers. Polymerization is carried out in the presence of a water-soluble graft-binding redox system. The use of chain transfer agents from the group consisting of mercaptans is described to adjust the molecular weight.
    [04] WO 2002/14393 A1 describes a process for the preparation of polymer dispersions that are used as sizing agents and coating materials. These polymer dispersions can be obtained by emulsion copolymerization of a monomer mixture comprising at least one C3-C8 (meth) acrylate, saturated monohydric alcohols, of at least another ethylenically unsaturated monomer in the presence of a starch or a starch derivative and an initiator comprising peroxide groups. Emulsion polymerization is distinguished by the fact that both the monomers and the initiator are introduced and measured continuously, a first quantity of initiator being introduced and measured within a first feeding period of from 5 to 60 minutes and a second quantity of initiator which is less than the first amount of initiator that is measured and introduced within a second feeding period of from 5 to 180 minutes. The use of chain transfer agents is not described.
    [05] Finely divided polymer dispersions, containing starch, as sizing agents for paper, cardboard and cardboard are also described in WO 2007/000419 A1. These can be obtained by emulsion polymerization in an aqueous medium, using redox initiators, ethylenically unsaturated monomers comprising (i) at least one optionally substituted styrene, methyl methacrylate, acrylonitrile and / or methacrylonitrile, (ii) by at least one C1-C12-alkyl (meth) acrylate and at least (iii) an ethylenically unsaturated copolymerizable monomer in the presence of a degraded cationic starch that has an Mw molar mass of from 1000 to 65,000 g / mol. The description comprises a large number of chain transfer agents, however the example according to the invention is carried out without a chain transfer agent.
    [06] WO 2007/000420 A1 likewise describes finely divided aqueous polymer dispersions, containing starch, as sizing agents for paper, cardboard and cardboard, which can be obtained free radical polymerization in (i) emulsion at least one optionally substituted styrene, methyl methacrylate, acrylonitrile and / or methacrylonitrile, (ii) at least one C1-C4-alkyl methacrylate, (iii) at least one C5-C22-alkyl (meth) acrylate and (iv ) optionally at least one other ethylenically copolymerizable monomer and (v) a degraded starch having a Mw molar mass of from 1000 to 65,000 in the presence of chain transfer agent. The specification describes a large number of potential chain transfer agents, but tert-dodecyl mercaptan is the preferred chain transfer agent, which is also used in all examples.
    [07] WO 2011/039185 describes finely divided aqueous polymer dispersions of starch-containing polymer which are obtained by free radical emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one redox and starch initiator. The polymers are formed by polymerizing at least one optionally substituted styrene, at least one C1-C12-alkyl acrylate or methacrylate and optionally another ethylenically unsaturated monomer. The polymerization employs at least one terpene-containing chain transfer agent.
    [08] There is a continuing need in the paper industry for new efficient mechanism sizing agents (also known as internal sizing agents) and surface sizing agents for the production of paper, cardboard and cardboard.
    [09] Thus, according to the present invention we provide a dispersion of finely divided polymer, containing starch, which can be obtained by free radical polymerization in emulsion of ethylenically unsaturated monomers in the presence of at least one redox and starch initiator, wherein (a) from 0 to less than 40% by weight of at least one optionally substituted styrene, (b) from more than 60 to 100% by weight of at least one C1-C12-alkyl acrylate and / or a C1-C12-alkyl methacrylate, (c) from 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer, are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% based on the content of active monomer and (d) from 15 to 40% by weight of at least one degraded starch that has a molar mass Mw of from 1000 to 65,000 g / mol, based on the total weight of content of solids from components (a) + (b) + (c) + (d), are used as starch and polymerization being carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least chain transfer agent, and wherein the polymer dispersion optionally comprises an aluminum compound.
    [10] The aqueous polymer dispersions, containing starch, finely divided according to the invention are distinguished by a significantly greater sizing effect compared to the prior art in the production of paper, cardboard and cardboard.
    [11] The monomers in group (a) are optionally substituted styrenes. This group includes styrene and substituted styrenes, such as, for example, α-methylstyrene, ring-halogenated styrenes, such as chloro-styrene or substituted C1-C4-styrenes, such as vinyltoluene. Of course, mixtures of optionally substituted styrenes can also be used. A monomer of this group used preferably is styrene, which is preferably used isolated from this group.
    [12] The monomers of group (a) are present in an amount of from 0 to less than 40% by weight, preferably from 1 to below 40% by weight, in the mixture of the ethylenically unsaturated monomer comprising (a) , (b) and (c). More preferably the monomers of group (a) can be present in an amount of at least 5% by weight, often at least 10%, typically at least 15% and often at least 20% or more, for example, at least 25% or more. Often the monomers in group (a) can be present in an amount of not more than 39% by weight and typically not more than 37% or 38%. Often monomers in this group can be present in an amount of up to 35%. More preferably, these monomers can be present in an amount of up to 30% and in some cases up to 25%. These amounts can be useful in combination with any of the ranges mentioned above. Typical ranges include 15 to 35% by weight and 20 to 35%.
    [13] Suitable monomers in group (b) are all esters of acrylic acid and methacrylic acid which are derived from C1-C12-monohydric alcohols, such as methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate sec-butyl acrylate, sec-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, neopentyl acrylate, neopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2- hexyl acrylate, 2- methacrylate hexyl, 2-ethylhexyl acrylate, 2-hexyl acrylate, n-octyl acrylate, 2-octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, decyl acrylate and decyl methacrylate, dodecyl acrylate, methacrylate , 2-propylheptyl acrylate and methacrylat that of 2-propylheptila. Preferably the monomers of this group used are esters of acrylic acid and methacrylic acid with C1-C8-alcohols, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylate of sec-butyl, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate. Acrylic acid esters with C1-C4-alcohols, such as n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate and tert-butyl acrylate are particularly preferred. Of these, tert-butyl acrylate is an example of an especially preferred monomer from this group.
    [14] According to the invention, at least one C1-C12-alkyl acrylate and / or C1-C12-alkyl methacrylate is used as a monomer of group (b), for example, two or more of the esters mentioned above in any desired mixtures with each other. Preferably only one monomer of the group (b) is used as a monomer of the group and particularly preferably a monomer of the group consisting of esters of acrylic acid with C1-C4-alcohols.
    [15] The monomers of group (b) are present in an amount of from more than 60 to 100% by weight in the mixture of ethylenically unsaturated monomer comprising (a), (b) and (c), preferably in quantities at least 61% and typically at least 62% or at least 63%. Often monomers in this group can be present in an amount of at least 65%. The monomers of group (b) can preferably be present in an amount of up to 99% by weight (for example, from 61% to 99%), suitably up to 95% and typically up to 85% or 90%. Often monomers in this category can be present in an amount of up to 75% or 80%. These amounts can be useful in combination with any of the ranges mentioned above. Typical ranges, for example, include 65 to 80% and 65 to 75%.
    [16] To modify the polymers, polymerization can optionally be carried out in the presence of at least one other monomer (c). Suitable monomers (c) are in principle all monomers that differ from monomers (a) and (b). Examples of such monomers are vinyl acetate, vinyl propionate, hydroxyethyl acrylate, hydroxyethyl methacrylate, N-viniformamide, acrylamide, methacrylamide, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam, acrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylonic acid styrenesulfonic acid, vinyl sulfonic acid and salts of monomers comprising acid groups. The acid monomers can be used in partially or completely neutralized form. The neutralizing agents used are, for example, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium bicarbonate, calcium hydroxide and ammonia.
    [17] Other examples of (c) monomers are diaminoalkyl and diaminoalkyl (meth) acrylamides (meth) acrylates, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylmethylmethylmethylmethylmethylmethylmethylmethylpropylmethylmethylamine, acrylamide, acrylamide dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminoproprylacrylamide and dimethylaminopropylmethacrylamide. Basic monomers can be used in the form of free bases, as salts with organic acids or with mineral acids or in quaternized form in polymerization.
    [18] In addition, linear or branched C1-C30-carboxylic acid vinyl esters are suitable as monomers of group (c). Such carboxylic acids are saturated and straight-chained, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capronic acid (hexanoic acid), heptanoic acid, caprylic acid (octanoic acid), pelargonic acid, capric acid ( decanoic acid), undecanoic acid, lauric acid (dodecanoic acid), tridecanoic acid, myristic acid (tetradecanoic acid), pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignocic acid ), kerotic acid, melissic acid (triacontanoic acid). According to the invention, saturated, branched carboxylic acids, such as isobutyric acid, isovaleric acid (3-methyl butyric acid) and tubercolostearic acid and strongly branched saturated carboxylic acids are also suitable. The latter are known by the term versatic acids, such as, for example, pivalic acid, neohexanoic acid, neoheptanoic acid, neooctanoic acid, neononanoic acid and neodecanoic acid. Suitable vinyl esters of straight or branched C1-C30-carboxylic acids are, for example, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate, vinyl acetate, vinyl propylheptanoate, vinyl neodecanoate (VeoVA® 10 from Hexion Specialty Chemicals), vinyl neononanoate (VeoVa® 9 from Hexion Specialty Chemicals) and vinyl pelargonate.
    [19] Of course, any desired mixtures of said monomers (c) can be used.
    [20] The monomers of group (c) are present in an amount of from 0 to 10% by weight in the mixture of ethylenically unsaturated monomer comprising components (a), (b) and (c). If these are used to modify the polymers, the amounts preferably used are from 0.1 to 5% by weight, based on the mixture of ethylenically unsaturated monomer comprising components (a), (b) and (c).
    [21] The polymerization of the monomers is carried out in the presence of a degraded starch as component (d), which has a Mw molar mass from 1000 to 65,000 g / mol. The average molecular weights Mw of the degraded starches can be easily determined by methods known to the person skilled in the art, for example, by means of gel permeation chromatography using a multi-angle light diffusion detector.
    [22] To obtain such a starch, it is possible to start from all types of starches, for example, from potato, corn, wheat, rice, tapioca, peas, sorghum or wax starch, which have a amylopectin content of> 80, preferably> 95% by weight, such as waxy corn starch and waxy potato starch. Starches can be modified, esterified, etherified and / or cross-linked anionically and / or cationically. Anionic starches are preferred.
    [23] If the Mw molecular weight of starches is no longer in the range from 1000 to 65,000 g / mol, they are subject to an increase in molecular weight before polymerization starts or in a separate step. A procedure in which a starch is degraded enzymatically and / or oxidatively before the start of polymerization is preferred. The Mw molar mass of the degraded starch is preferably in the range from 2,500 to 35,000 g / mol.
    [24] In the case of cationized starches, these are prepared, for example, by reacting native starch with at least one quaternizing agent, such as 2,3-epoxypropyltrimethylammonium chloride. Cationized starches comprise groups of quaternary ammonium.
    [25] In the case of anionic starches, these are obtained, for example, by oxidation reaction of native starch with a suitable oxidizing agent, such as hypochlorite or sodium periodate.
    [26] The proportion of cationic or anionic groups in the substituted starch is established with the help of the degree of substitution (DS). This is, for example, from 0.005 to 1.0, preferably from 0.01 to 0.4.
    [27] All starches can be used. The degradation of starches is preferably carried out before the polymerisation of the monomers, but it can also be carried out during the polymerisation of the monomers. It can be carried out by oxidation, thermally, acidolytically or enzymatically. Preferably, the degradation of the starch is carried out enzymatically and / or by oxidation directly before the start of the emulsion polymerization in the apparatus where the polymerization needs to be carried out or in a separate step. It is possible to use a single degraded starch or mixtures of two or more degraded starches in the polymerization.
    [28] Starch is present in the reaction mixture comprising components (a), (b), (c) and (d) in an amount of from 15 to 40% by weight based on the total weight of the solids content , preferably from 25 to 35% by weight.
    [29] The polymer dispersions, containing starch, finely divided according to the invention can be obtained by carrying out the polymerization in the presence of at least 0.01% by weight, based on the monomers used, of at least one transfer agent chain containing terpene also known as polymerization regulators.
    [30] It is understood that chain transfer agents can be chain transfer agents that contain terpenes as meaning those hydrocarbons that are composed of isoprene units [H2C = C (CH3) -CH = CH2] and can therefore be derived from the isoprene rule. Terpenes are divided into monoterpenes (C10), sesquiterpenes (C15), diterpenes (C20), sesterterpenes (C25), triterpenes (C30) and tetraterpenes (C40) and polyterpenes (> C40), substantially into acyclic, bicyclic and tricyclic terpenes. Terpenes are known to a person skilled in the art, for example, by Rompp Chemie Lexikon, 9a. Extended and revised edition, 1989-1992, Georg Thieme Verlag Stuttgart.
    [31] In the broadest sense, terpenes are understood to mean hydrocarbons having a C10H16 skeleton and the hydrogenation and dehydrogenation derivatives thereof and the alcohols, ketones, aldehydes and esters derived therefrom.
    [32] According to the invention, preferably monocyclic monoterpenes are used, particularly preferably di-unsaturated monocyclic monoterpenes (so-called p-mentadienes). Examples of di-unsaturated monocyclic monoterpenes are α-, β- and Y — terpinene, terpinolene, (+) - (S) -α-felandreno, (-) - (S) -α-felandreno and limonene. Α-terpinene and terpinolene are preferred and terpinolene is particularly preferred.
    [33] Of course, mixtures of said terpene-containing chain transfer agents may also be used, however, preferably only one chain transfer agent containing terpene is used, particularly preferably only terpinolene is used.
    [34] Terpene-containing chain transfer agents are used in a polymerization in an amount of at least 0.01% by weight, based on the monomers. The amounts depend substantially on the efficiency of the chain transfer agent or chain transfer agents used in each case. They are usually in the range of from 0.01 to 10% by weight, preferably from 0.05 to 5.0% by weight, based on monomers (a), (b) and (c).
    [35] To initiate polymerization, a redox initiator according to the invention is used. Said redox initiators are preferably graft-binding water-soluble redox systems, for example, which comprise hydrogen peroxide and a heavy metal salt or which comprise hydrogen peroxide and sulfur dioxide or which comprise hydrogen peroxide and sodium metabisulphite. Other suitable redox systems are combinations of tert-butyl hydroperoxide / sulfur dioxide, sodium or potassium persulfate / sodium bisulfite, ammonium persulfate / sodium bisulfite or ammonium persulfate / iron (II) sulfate. Preferably, hydrogen peroxide is used in combination with a heavy metal salt, such as iron (II) sulfate. Often, the redox system further comprises another reducing agent, such as ascorbic acid, sodium formaldehyde sulfoxylate, sodium disulfite or sodium dithionite. As the polymerization of monomers is carried out in the presence of starch and as starch acts in the same way as a reducing agent, the concomitant use of other reducing agents is generally dispensed with. Redox initiators are used, for example, in an amount of from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, based on the monomers.
    [36] In some circumstances it would be desirable to provide starch sizing compositions that exhibit better storage stability. Unexpectedly, it was found that by including at least one aluminum compound, storage stability can be improved without deleterious effects on sizing performance. In addition, it has also been found that in some circumstances starch-based sizing compositions of the present invention that additionally contain at least one aluminum compound can exhibit improved sizing effects.
    [37] Thus, the polymer dispersions of the present invention desirably can also contain at least one aluminum compound. This aluminum compound will desirably be included in the polymer dispersion that has formed.
    [38] Typically the aluminum compound can be any suitable compost that does not adversely vary the properties of the polymer dispersion. In general, the aluminum compound can be a water-soluble compound. Suitable aluminum compounds include aluminum sulfate, aluminum chloride, aluminum phosphate, aluminum nitrate, aluminum hydroxide, aluminum oxide and aluminum polychloride. Preferred aluminum compounds include aluminum sulfate and aluminum polychloride.
    [39] Typically the aluminum compound can be included in an amount of at least 0.1% by weight based on the weight of the total solids content of the dispersion. The amount can be as much as 60 or 70% by weight but generally it will be up to 50%. Other suitable ranges include at least 1% or at least 2% or at least 5% or, for example, up to 30% or up to 40%.
    [40] Consequently, polymer dispersions that can be obtained by free radical polymerization in emulsion of ethylenically unsaturated monomers in the presence of at least one redox and starch initiator, are preferred (a) from 0 to less than 40% in weight of at least one optionally substituted styrene, (b) from more than 60 to 100% by weight of at least one C1-C12-alkyl acrylate and / or a C1-C12-alkyl methacrylate, (c) from 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% based on the active monomer content and (d ) from 25 to 35% by weight of at least one degraded starch having a molar mass Mw of from 1000 to 65,000 g / mol, based on the total weight of the solids content of components (a) + (b) + (c ) + (d), are used as starch, and polymerization is carried out in the presence of at least 0.01% by weight, based on in the monomers used, at least one terpene-containing chain transfer agent, and wherein the polymer dispersion optionally comprises 0.1 to 50% of an aluminum compound based on the total weight of the solids content of the polymer dispersion.
    [41] Particularly preferred finely divided polymer dispersions containing starch are those which (a) from 15 to 35% by weight of at least one optionally substituted styrene, (b) from 65 to 80% by weight of an acrylate of C1-C12-alkyl and / or a C1-C12-alkyl methacrylate, (c) from 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% based on the active monomer content and (d) from 25 to 35% by weight of at least one degraded starch that has a Mw molar mass of from 2,500 to 35,000 g / mol , based on the total weight of the solids content of the components (a) + (b) + (c) + (d), are used as the starch, and polymerization is carried out in the presence of at least 0.01% by weight , based on the monomers used, of at least one chain transfer agent containing terpene, and wherein the polymer dispersion optionally comprises 0.1 to up to 50% of an aluminum compound based on the total weight of the solids content of a polymer dispersion.
    [42] In particular, those finely divided starch-containing polymer dispersions are preferred in which (a) from 20 to 35% by weight of at least one optionally substituted styrene, (b) from 65 to 75% by weight of a C1-C12-alkyl acrylate, (c) from 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being of 100% based on the active monomer content and (d) from 25 to 35% by weight of a degraded anionic starch which has a Mw molar mass of from 2,500 to 35,000 g / mol, based on the total weight of the solids content of the components (a) + (b) + (c) + (d), are used as the starch, and polymerization is carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least a terpene-containing chain transfer agent, and wherein the polymer dispersion optionally comprises 0.1 to 50% aluminum compound with based on the total weight of the solids content of the polymer dispersion.
    [43] It is especially preferred that in the polymer dispersion, containing starch, finely divided (a) from 20 to 35% by weight of at least one optionally substituted styrene, (b) from 65 to 75% by weight of a C1 acrylate -C4-alkyl, (c) from 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% with based on the active monomer content and (d) from 25 to 35% by weight of a degraded anionic starch that has a Mw molar mass of from 2,500 to 35,000 g / mol, based on the total weight of the components' solids content (a ) + (b) + (c) + (d), are used as the starch, and polymerization is carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least one transfer agent chain containing terpene, and where the polymer dispersion optionally comprises 0.1 to 50% of an aluminum compound based on the total weight of the solids content of the polymer dispersion.
    [44] The invention also relates to a process for the preparation of polymer dispersions, containing starch, finely divided according to the invention which can be obtained by emulsion polymerization.
    [45] Such a process is distinguished by the fact that (a) from 0 to less than 40% by weight of at least one optionally substituted styrene, (b) from more than 60 to 100% by weight of at least by weight of a C1-C12-alkyl acrylate and / or a C1-C12-alkyl methacrylate, (c) from 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer, are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% based on the active monomer content and (d) from 15 to 40% by weight of at least one degraded starch that has a Mw molar mass of from 1000 up to 65,000 g / mol, based on the total weight of the solids content of the components (a) + (b) + (c) + (d), are polymerized in the presence of a redox initiator in an aqueous medium and polymerization is carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least one chain transfer agent containing terpene, and in which the polymer dispersion o optionally comprises an aluminum compound.
    [46] Emulsion polymerization of monomers (a) to (c) is carried out in an aqueous medium in the presence of a starch (d) which has a Mw molar mass from 1000 to 65,000 g / mol. Monomers can be polymerized by the emulsion polymerization method, either in the feeding procedure or in the batch procedure. Preferably, an aqueous solution of the degraded starch and a heavy metal salt is initially used and the monomers are added separately or as a mixture and, separately from it, the oxidizing part of the redox initiator, preferably hydrogen peroxide, is added continuously or in batch. A gradient procedure, which is described in WO 2002/14393 A1, can also be used for the preparation of polymer dispersions containing starch.
    [47] The addition can be done uniformly or non-uniformly, that is, with the measurement rate of variation, during the measurement period.
    [48] Polymerization is usually carried out in the absence of oxygen, preferably in an inert gas atmosphere, for example, under nitrogen. During polymerization, a very well-made mixture of the components needed to be guaranteed. In this way, the reaction mixture is preferably stirred throughout the polymerization and any subsequent postpolymerization.
    [49] Polymerization is usually carried out at temperatures from 30 to 110 ° C, preferably from 50 to 100 ° C. The use of a pressure-resistant reactor or the realization of a continuous flow in an agitated tank cascade or in a drainpipe is also possible.
    [50] To improve the dispersion effect, customary ionic, non-ionic or amphoteric emulsifiers can be added to a batch of polymerization. Ordinary emulsifiers are used only optionally. The amounts used are from 0 to 3% by weight and are preferably in the range of from 0.02 to 2% by weight, based on the sum of the monomers (a), (b) and (c) used. Ordinary emulsifiers are described in detail in the literature, cf. , for example, M. Ash, I. Ash, Handbook of Industrial Surfactants, Third edition, Synapse Information Resources Inc. Examples of customary emulsifiers are the products of the reaction of long chain monohydric alcohols (C10- to C22-alkanols) with 4 to 50 moles of ethylene oxide and / or propylene oxide per mole of alcohol or ethoxylated phenols or alkoxylated alcohols esterified with sulfuric acid which are generally used in the form neutralized with alkali. Other customary emulsifiers are, for example, sodium alkanesulfonates, sodium alkyl sulfates, sodium dodecylbenzenesulfonate, sulfosuccinic esters, quaternary alkylammonium salts, alkylbenzylammonium salts, such as dimethyl-C12- to C18-alkylsamines, amines, alkylenes, amines, alkylenes, amines, amines, amines, amines and amines. , secondary and tertiary, quaternary amidoamine compounds, alkylpyridinium salts, alkylimidazoline salts and alkyloxyazoline salts.
    [51] During emulsion polymerization, monomers can be measured and introduced directly to the mixture used initially, or they can be added in the form of an aqueous emulsion or a mini emulsion to a batch of polymerization. For this purpose, the monomers are emulsified in water using the usual emulsifiers mentioned above.
    [52] Polymerization is carried out at a pH of from 2 to 9, preferably in the weakly acidic range at a pH of 3 to 5.5. The pH can be adjusted to the desired value before or during polymerization with customary acids, such as hydrochloric acid, sulfuric acid or acetic acid or with bases, such as sodium hydroxide solution, potassium hydroxide solution, ammonia, carbonate of ammonium etc. The dispersion is preferably adjusted to a pH of from 3 to 5.5 after the end of the polymerization.
    [53] To remove residual monomers as substantially as possible from the polymer dispersion, containing starch, postpolymerization is conveniently carried out. For this purpose, an initiator from the group consisting of hydrogen peroxide, peroxides, hydroperoxides and / or azo initiators is added to a polymer dispersion after the end of the main polymerization. The combination of initiators with suitable reducing agents such as, for example, ascorbic acid or sodium bisulfite, is possible in the same way. Oil-soluble initiators that are sparingly soluble in water are preferably used, for example, customary organic peroxides, such as dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumila hydroperoxide or bisciclohexila peroxodicarbonate .
    [54] For post-polymerization, the reaction mixture is heated, for example, to a temperature that corresponds to the temperature at which the main polymerization was carried out or that is up to 20 ° C, preferably up to 10 ° C, taller. The main polymerization is complete when a polymerization initiator has been consumed or the monomer conversion is, for example, at least 98%, preferably at least 99.5%. The tert-butyl hydroperoxide is preferably used for postpolymerization. Postpolymerization is carried out, for example, in the temperature range from 35 to 100 ° C, in general from 45 to 95 ° C.
    [55] After the end of the polymerization, a complex forming agent for heavy metal ions can be added to a polymer dispersion in an amount such that all the metal ions are linked as a complex.
    [56] Starch-containing polymer dispersions comprise dispersed particles having an average particle size of from 20 to .500 nm, preferably from 50 to 250 nm. The average particle size can be determined by methods known to the person skilled in the art, such as, for example, laser correlation spectroscopy, ultracentrifugation or HDF (hydrodynamic fractionation). Another measure of the particle size of the dispersed polymer particles is the LT value. For the determination of the LT (light transmittance) value, the polymer dispersion to be investigated in each case is measured in an aqueous dilution with a concentration of 0.1% by weight in a cell that has an edge length of 2 , 5 cm that uses 600 nm wavelength light and is compared with the corresponding water transmittance under the same measurement conditions. Water transmittance is specified as 100%. The more finely divided the dispersion, the higher the LT value that is measured by the method described above. Starting from the measured values, it is possible to calculate the average particle size, cf. B. Verner, M. Bárta, B. Sedlácek, Tables of Scattering Functions for Spherical Particles, Prague, 1976, Edice Marco, Rada D-DATA, SVAZEK D-1.
    [57] The solids content of the polymer dispersion, containing starch, is, for example, from 5 to 50% by weight and is preferably in the range of from 15 to 40% by weight.
    [58] The finely divided polymer dispersions containing starch described above are used as sizing agents for paper, cardboard and cardboard. They can be used both as surface sizing agents and motor sizing agents in the amounts customary in each case. Use as a surface sizing agent is preferred. In this case, the dispersions according to the invention can be processed by all suitable methods in the case of surface sizing. The polymer dispersions can be applied to the surface of the paper to be glued, for example, by means of a sizing press, a film press or a roll opening applicator. For use, the dispersion is usually added to the press solution with sizing agent in an amount of from 0.05 to 3% by weight, based on the solid substance and depends on the desired degree of sizing of the papers to be finished. In addition, the sizing agent press solution may comprise other substances, such as, for example, starch, pigments, dyes, optical brightening agents, biocides, paper reinforcing agents, fixing agents, defoamers, retention aids and / or drainage aids. The amounts of polymer that are applied to the surface of paper products are, for example, from 0.005 to 1.0 g / m2, preferably from 0.01 to 0.5 g / m2. Compared with known sizing agents, sizing agents according to the invention have the advantage that they provide a better sizing effect even when applied in small quantities, especially on uncoated wood-free papers.
    [59] The invention is explained in more detail with reference to the following non-limiting examples. EXAMPLES
    [60] The percentage data in the examples are in percent weight, unless otherwise evident from the context.
    [61] LT values were determined in aqueous solution with a concentration of 0.1% of a dispersion to be determined, using a Hach DR / 2010 apparatus at a wavelength of 600 nm. Particle sizing agents were determined using a high performance particle size (HPPS) by Malvern using a He-Ne laser (633 nm) at a diffusion angle of 173 °. Example 1 Dispersion 1
    [62] In a 2-liter ground-glass flask equipped with a stirrer and internal temperature measurement, 75.00 g of oxidative degraded starch (80% by weight) with a COO-- substitution degree of 0.03 - 0.04 and a K value of 34 (determined according to DIN 53726) (Amylex® 15 from Co. Südstarke) and 370.00 g of demineralized water were added to the load and heated to 80 ° C with stirring within 1 hour. Then 120 liters of a solution of 1.40 g (1% by weight) of Temamyl enzyme were added and the mixture was stirred for 20 minutes. Thereafter, 4.00 g (10% by weight) of iron (II) sulfate solution was added, heptahydrated in water, and enzymatic degradation was stopped. Subsequently, 70.00 g (5% by weight) of hydrogen peroxide solution was started and fed for 165 minutes. Concomitantly a mixture of 42.00 g of Styrene, 98.00 g of tert-butyl acrylate, 1.00 g of Terpinolene (90% by weight), 0.50 g (40% by weight) of Emulsifier K30 (Na -C14-C15-alkylsulfonate, Emulgator® K30 from Bayer AG) and 110.00 g of demineralized water were also fed for 120 minutes. After starting both feeds, the reaction temperature was raised to 85 ° C within 5 minutes. At the end of the monomer feed, 15.00 g of demineralized water were added. 15 minutes after the hydrogen peroxide feed was completed, 2.00 g (10% by weight) of tert-butyl hydroxide and 1.00 g of a 10% by weight solution of ascorbic acid were added and stirred for 15 minutes. minutes, followed by a further addition of 2.00 g (10% by weight) of tert-butyl hydroxide. The batch was further stirred for 30 minutes and then cooled to room temperature. A finely divided polymer dispersion was obtained which has a solids content of 26% by weight, an LT value (0.1%) of 83.4% and a particle size of 76 nm. Comparative Example 1 Dispersion 2
    [63] In a 2-liter ground-glass flask equipped with a stirrer and internal temperature measurement, 75.00 g of oxidative degraded starch (80% by weight) with a COO substitution degree— 0.03 - 0.04 and a K value of 34 (determined according to DIN 53726) (Amylex® 15 from Co. Südstarke) and 370.00 g of demineralized water were added to the load and heated to 80 ° C with stirring within 1 hour. Then 120 liters of a solution of 1.40 g (1% by weight) of Temamyl enzyme were added and the mixture was stirred for 20 minutes. Thereafter, 4.00 g (10% by weight) of iron (II) sulfate solution, heptahydrate in water were added and the enzymatic degradation was stopped. Subsequently the solution feed with 70.00 g (5% by weight) of hydrogen peroxide was started and fed for 165 minutes. Concomitantly a mixture of 42.00 g of Styrene, 98.00 g of tert-butyl acrylate, 0.50 g (40% by weight) of Emulsifier K30 (Na-C14-C15-alkylsulfonate, Emulgator® K30 from Bayer AG ) and 110.00 g of demineralized water were also fed for 120 minutes. After starting both feeds, the reaction temperature was raised to 85 ° C within 5 minutes. At the end of the monomer feed, 15.00 g of demineralized water were added. 15 minutes after completing the hydrogen peroxide feed, 2.00 g (10% by weight) of tert-Butylhydroperoxide and 1.00 g of a 10% by weight ascorbic acid solution were added and stirred for 15 minutes, followed by a further addition of 2.00 g (10% by weight) of tert-Butylhydroperoxide. The batch was further stirred for 30 minutes and then cooled to room temperature. A finely divided polymer dispersion was obtained which has a solids content of 25% by weight, an LT value (0.1%) of 73% and a particle size of 73 nm. Example 2 Dispersion 3
    [64] In a 2-liter ground-glass flask fitted with a stirrer and internal temperature measurement, 73.62 g of Avecat 15 cationic starch (81.5% by weight), 0.75 g (1% by weight) ) of enzyme solution Temamyl 120 L) and 370.00 g of demineralized water were added to the load and heated to 80 ° C with stirring within 1 hour. Then 7.50 g (1 wt%) of Temamyl 120 L enzyme solution was added and the mixture was stirred for 20 minutes. Thereafter, 4.00 g (10% by weight) of iron (II) sulfate solution, heptahydrate in water were added, and the enzymatic degradation was stopped. Subsequently, 70.00 g (5% by weight) of hydrogen peroxide solution was started and fed for 165 minutes. After initiating the initiator feed, the reaction temperature was raised to 85 ° C within 5 minutes and 10 minutes later a mixture of 42.00 g of Styrene, 98.00 g of tert-butyl acrylate, 1.00 g of Terpinolene (90% by weight), 0.50 g (40% by weight) of Emulsifier K30 (Na-C14-C15-alkylsulfonate, Emulgator® K30 from Bayer AG) and 110.00 g of demineralized water was also started and fed for 120 minutes. At the end of the monomer feed, 15.00 g of demineralized water were added. 15 minutes after completing the hydrogen peroxide feed, 2.00 g (10% by weight) of tert-Butylhydroperoxide and 1.00 g of a 10% by weight ascorbic acid solution were added and stirred for 15 minutes, followed by a further addition of 2.00 g (10% by weight) of tert-Butylhydroperoxide. The batch was further stirred for 30 minutes and then cooled to room temperature. A finely divided polymer dispersion was obtained which has a solids content of 25.25% by weight, an LT value (0.1%) of 81% and a particle size of 72 nm. Comparative Example 2 Dispersion 4
    [65] In a 2-liter ground-glass flask equipped with a stirrer and internal temperature measurement, 73.62 g of Avecat 15 cationic starch (81.5% by weight), 0.75 g (1%) were added by weight) of Temamyl 120 L enzyme solution) and 370.00 g of demineralized water were added to the load and heated to 80 ° C with stirring within 1 hour. Then 7.50 g (1% by weight) of Temamyl 120L enzyme solution was added and the mixture was stirred for 20 minutes. Thereafter, 4.00 g (10% by weight) of iron (II) sulfate solution, heptahydrate in water were added, and the enzymatic degradation was stopped. Subsequently, 70.00 g (5% by weight) of hydrogen peroxide solution was started and fed for 165 minutes. After starting the initiator feed, the reaction temperature was raised to 85 ° C within 5 min and 10 minutes later a mixture of 42.00 g of Styrene, 98.00 g of tert-butyl acrylate, 0 , 50 g (40% by weight) of Emulsifier K30 (Na-C14-C15-alkylsulfonate, Emulgator® K30 from Bayer AG) and 110.00 g of demineralized water and fed for 120 minutes. At the end of the monomer feed, 15.00 g of demineralized water were added. 15 minutes after the hydrogen peroxide feed was completed, 2.00 g (10% by weight) of tert-Butylhydroperoxide and 1.00 g of a 10% by weight ascorbic acid solution were added and stirred for 15 minutes, followed by a further addition of 2.00 g (10% by weight) of tert-Butylhydroperoxide. The batch was further stirred for 30 minutes and then cooled to room temperature. The finely divided polymer dispersion, which has a solids content of 24.7% by weight, obtained an LT value (0.1%) of 72.3% and a particle size of 82 nm. Comparative Example 3 Dispersion 5
    [66] In a 2 l ground-glass flask fitted with a stirrer and internal temperature measurement, 75.00 g of oxidative degraded starch (80% by weight) with a COO- substitution degree of 0 were added, 03 - 0.04 and a K value of 34 (determined according to DIN 53726) (Amylex® 15 from Co. Südstarke) and 370.00 g demineralized water were added to the load and heated to 80 ° C under agitation. Then 1.40 g (1% by weight) of Temamyl 120 L enzyme solution was added and the mixture was stirred for 20 minutes. Thereafter, 4.00 g (10% by weight) of iron (II) sulfate solution, heptahydrate in water were added, and the enzymatic degradation was stopped. Subsequently the feeding of 68.00 g (5% by weight) of hydrogen peroxide solution was started and fed for 165 minutes. Concomitantly, a mixture of 92.00 g of Styrene, 46.00 g of n-butyl acrylate, 1.50 g of Acrylic acid, 0.6 g of Terpinolene (90% by weight), 0.50 g (40% by weight) of Emulsifier K30 (Na-C14-C15-alkylsulfonate, Emulgator® K30 from Bayer AG) and 110.00 g of demineralized water were also fed for 120 minutes. After starting both feeds, the reaction temperature was raised to 85 ° C within 5 minutes. At the end of the monomer feed, 15.00 g of demineralized water were added. 15 min after the hydrogen peroxide feed was completed, 2.00 g (10% by weight) of tert-Butylhydroperoxide was added and stirred for 30 minutes and finally cooled to room temperature. A finely divided polymer dispersion was obtained which has a solids content of 25.3% by weight, an LT value (0.1%) of 79.5% and a particle size of 70 nm. Comparative Example 4 Dispersion 6
    [67] In a 2-liter ground-glass flask equipped with a stirrer and internal temperature measurement, 79.55 g of oxidative degraded starch (80% by weight) with a COO substitution degree of 0 was added , 03 - 0.04 and a K value of 34 (determined according to DIN 53726) (Amylex® 15 d Co. Südstarke) and 430.00 g demineralized water were added to the load and heated to 85 ° C with stirring. Then 2.30 g (1 wt%) of Temamyl enzyme solution 120 L and 1.02 g (25 wt%) of hydrated calcium acetate were added and the mixture was stirred for 30 minutes. Thereafter 2.6 g (10% by weight) of iron (II) sulphate solution heptahydrate in water and 9.22 g of acetic acid were added, and the enzymatic degradation was stopped. Subsequently 4.45 g (5% by weight) of hydrogen peroxide solution was added in 1 minute and also 40.05 g of the same hydrogen peroxide solution was started and fed for 120 minutes. Concomitantly the mixture of 84.64 g of Styrene, 42.32 g of tert-butyl acrylate, 42.32 g of 2-ethylhexyl acrylate, 2.30 g of tert-dodecylmercaptan, 0.20 g (40 % by weight) of Emulsifier K30 (Na-C14-C15-alkylsulfonate, Emulgator® K30 from Bayer AG) and 124.17 g of demineralized water were also fed for 90 minutes. At the end of the peroxide feed, the reaction mixture was further stirred for 30 minutes and cooled to 50 ° C. Then 2.19 g (10% by weight) of tert-Butylhydroperoxide was added and stirred for 30 minutes followed by cooling to room temperature. At this temperature, 28.94 g (25% by weight) of sodium hydroxide was added over 5 minutes and finally 100 g of demineralized water were added. A polymer dispersion was obtained which has a solids content of 24.3% by weight, an LT value (0.1%) of 67.2% and a particle size of 72 nm. Comparative Example 5 Scatter 7
    [68] In a 2-liter ground-glass flask fitted with a stirrer and internal temperature measurement, 77.15 g of oxidative degraded starch (80% by weight) with a COO substitution degree-- of 0 was added , 03 - 0.04 and a K value of 34 (determined according to DIN 53726) (Amylex® 15 from Co. Südstarke) and 159.65 g DE demineralized water were added to the load and heated to 85 ° C within 45 minutes under agitation. Then 5.40 g (1% by weight) of Temamyl enzyme solution 120L and 0.86 g (25% by weight) of hydrated calcium acetate were added and the mixture was stirred for 30 minutes. Thereafter 17.10 g (1% by weight) of a solution in water of iron (II) sulphate heptahydrate and 8.57 g of acetic acid were added, and the enzymatic degradation was stopped. Subsequently 22.72 g (30% by weight) of hydrogen peroxide solution was fed for 30 minutes and still 5.68 g of the same hydrogen peroxide solution was fed for 75 minutes. Concomitantly with the peroxide feed the mixture of 105.00 g of Styrene, 45.00 g of n-butyl acrylate, 2.70 g (40% by weight) of Emulsifier K30 (Na-C14-C15-alkylsulfonate, Emulgator ® K30 from Bayer AG) and 53.57 g of demineralized water were also fed for 90 minutes. At the end of the peroxide feed the reaction mixture is cooled to room temperature. At this temperature the pH was adjusted with sodium hydroxide to a pH value of 5. A polymer dispersion was obtained which has a solids content of 32.9% by weight, an LT value (0.1%) of 3.4% and a particle size of 372 nm. Example 3 Dispersion 8
    [69] In a 2-liter ground-glass flask equipped with a stirrer and internal temperature measurement, 72.29 g of cationic Lyckeby PU-11597 starch (83% by weight) and 370.00 g of demineralized water were added were added to the load and heated to 80 ° C with stirring within 1 hour. Then 7.70 g (1% by weight) of Temamyl 120 L enzyme solution was added and the mixture was stirred for 20 minutes. Thereafter, 4.00 g (10% by weight) of iron (II) sulphate solution, heptahydrate were added, and the enzymatic degradation was stopped. Subsequently, 70.00 g (5% by weight) of hydrogen peroxide solution was started and fed for 165 minutes. After initiating the initiator feed, the reaction temperature was raised to 85 ° C within 5 min and 10 minutes later the mixture of 42.00 g of Styrene, 98.00 g of tert-butyl acrylate, 1.00 g of Terpinolene (90% by weight), 0.50 g (40% by weight) of Emulsifier K30 (Na-C14-C15-alkylsulfonate, Emulgator® K30 from Bayer AG) and 110.00 g of demineralized water was also started and fed for 120 minutes. At the end of the monomer feed, 15.00 g of demineralized water were added. 15 min after completing the hydrogen peroxide feed, 2.00 g (10% by weight) of tert-Butylhydroperoxide and 1.00 g of a 10% by weight ascorbic acid solution were added and stirred for 15 minutes, followed by a further addition of 2.00 g (10% by weight) of tert-Butylhydroperoxide. The batch was further stirred for 30 minutes and then cooled to room temperature. The finely divided polymer dispersion was obtained which has a solids content of 24.7% by weight, an LT value (0.1%) of 84.3% and a particle size of 67 nm. Example 4 Mix 1
    [70] The dispersion of example 3 (Dispersion 8) was combined with aluminum sulfate at a ratio of 3: 1 by weight. Example 5 Mix 2
    [71] The dispersion of Example a (Dispersion a) was combined with aluminum sulfate at a ratio of 3: 1 by weight.
    [72] Testing of the performance characteristics of the polymer dispersions obtained according to the examples and the Comparative Examples
    [73] An aqueous solution of a degraded corn starch was adjusted to the desired concentration. The dispersions of the examples and the Comparative Example that needed to be tested were then measured and introduced into the starch solution so that the sizing press solution comprised 100 g / l of a degraded corn starch and 1-3 g / l of the respective starch. dispersal. The mixture of starch solution and polymer dispersion was then applied by means of a sizing press to a paper that has a weight of 80 g / m2, which was slightly pre-pasted on the pulp with AKD (alkyldethylene), at a temperature 50 ° C. The uptake of the preparation was in the region of around 45%. After that, the papers treated in this way were dried by means of contact drying at 90 ° C, conditioned for 24 hours at 50% atmospheric humidity and then subjected to tests.
    [74] The test paper used was a paper that was slightly precollaged in the pulp with AKD and had the following composition: fiber composition (80% bleached birch sulphate pulp and 20% bleached pine sulphate pulp ) which has a charge content of 19% (Hydrocarb® 60ME from Omya)
    [75] To determine the degree of sizing of the papers glued to the surface, the Cobb value was determined according to DIN EN 20 535. The water absorbing the paper sheet in g / m2 after contact with water and a time 60 s (or 120 s) contact is defined as the Cobb60 (or Cobb120) value. The lower the Cobb value, the better the sizing effect of a used dispersion.
    [76] The test results for the dispersions corresponding to Examples 1 and 2 and Comparative Examples 1 to 5 using amounts of 0.5, 0.6 and 0.8 g / l of solids respectively are summarized in Table 1. The tests for the dispersions corresponding to Examples 1 to 5 and Comparative Example 2 using amounts of 0.3, 0.4 and 0.5 g / l respectively were carried out on a different day and the results are summarized in Table 2. Table 1: Results of testing the performance characteristics
    Table 2

    [77] The results demonstrate that the best global sizing effect measured by the values of Cobb60 and Cobb120 are achieved by the examples of the invention. In addition, table 2 shows that dispersions containing an aluminum compound exhibit even better sizing.
    权利要求:
    Claims (16)
    [0001]
    1. A finely divided polymer dispersion containing starch that can be obtained by free radical polymerization in an emulsion of ethylenically unsaturated monomers in the presence of at least one redox and starch initiator, characterized by the fact that (a) from 15 to 35 % by weight of at least one optionally substituted styrene, (b) from more than 65 to 85% by weight of at least one C1-C12-alkyl acrylate and / or a C1-C12-alkyl methacrylate, (c) from 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer, are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% based on the active monomer content and (d) from 15 to 40% by weight of at least one degraded starch that has a molar mass Mw of from 1000 to 65,000 g / mol, based on the total weight of solids content of components (a) + (b) + (c) + (d), are used as starch, and polymerization being carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least one chain transfer agent, and wherein the polymer dispersion optionally comprises an aluminum compound.
    [0002]
    2. Polymer dispersion, containing starch, finely divided according to claim 1, characterized by the fact that (a) from 15 to 35% by weight of at least one optionally substituted styrene, (b) from more than 65 to 85% by weight of at least one C1-C12-alkyl acrylate and / or a C1-C12-alkyl methacrylate, (c) from 0 to 5% by weight of at least another ethylenically unsaturated copolymerizable monomer are used as the monomers ethylenically unsaturated, the sum of (a) + (b) + (c) being 100% based on the active monomer content and (d) from 25 to 35% by weight of at least one degraded starch that has a molar mass Mw from 1000 to 65,000 g / mol, based on the total weight of the solids content of the components (a) + (b) + (c) + (d), are used as the starch, and polymerization is carried out in the presence at least 0.01% by weight, based on the monomers used, at least one terpene-containing chain transfer agent, and where the polymer dispersion optionally comprises from 0.1 to 50% of an aluminum compound based on the total weight of the solids content of the polymer dispersion.
    [0003]
    3. Polymer dispersion, containing starch, finely divided according to claim 1 or 2, characterized by the fact that (a) from 15 to 35% by weight of at least one optionally substituted styrene, (b) from 65 to 80 % by weight of a C1-C12-alkyl acrylate and / or a C1-C12-alkyl methacrylate, (c) from 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% based on the active monomer content and (d) from 25 to 35% by weight of at least one degraded starch that has a Mw molar mass of from 2,500 up to 35,000 g / mol, based on the total weight of the solids content of the components (a) + (b) + (c) + (d), are used as the starch, and polymerization is carried out in the presence of at least 0 , 01% by weight, based on the monomers used, of at least one terpene-containing chain transfer agent, and in which the polymer dispersion optionally comprises it comprises 0.1 to 50% of an aluminum compound based on the total weight of the solids content of the polymer dispersion.
    [0004]
    4. Polymer dispersion, containing starch, finely divided according to any one of the preceding claims, characterized by the fact that (a) from 20 to 35% by weight of at least one optionally substituted styrene, (b) from 65 to 75 % by weight of a C1-C12-alkyl acrylate, (c) from 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% based on the active monomer content and (d) from 25 to 35% by weight of a degraded anionic starch that has a Mw molar mass of from 2,500 to 35,000 g / mol, based on the total weight of the solids content of components (a) + (b) + (c) + (d), are used as starch, and polymerization is carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least one terpene-containing chain transfer agent, and wherein the polymer dispersion optionally comprises 0.1 to 50% of an aluminum compound based on the total weight of the solids content of the polymer dispersion.
    [0005]
    5. Polymer dispersion, containing starch, finely divided according to any of the preceding claims, characterized by the fact that (a) from 20 to 35% by weight of at least one optionally substituted styrene, (b) from 65 to 75% by weight of a C1-C4-alkyl acrylate, (c) from 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer are used as the ethylenically unsaturated monomers, the sum of (a) + (b) + ( c) being 100% based on the content of active monomer and (d) from 25 to 35% by weight of a degraded anionic starch that has a Mw molar mass from 2,500 to 35,000 g / mol, based on the total weight of the solids content of components (a) + (b) + (c) + (d), are used as starch, and polymerization is carried out in the presence of at least 0.01% by weight, based on the monomers used, at least one terpene-containing chain transfer agent, and wherein the polymer dispersion optionally comprises 0.1 to 50% d and an aluminum compound based on the total weight of the solids content of the polymer dispersion.
    [0006]
    6. Polymer dispersion, containing starch, finely divided according to any one of the preceding claims, characterized by the fact that the terpene-containing chain transfer agent is used in an amount of from 0.01 to 10% by weight, with based on monomers.
    [0007]
    7. Polymer dispersion, containing starch, finely divided according to any one of the preceding claims, characterized by the fact that the terpene-containing chain transfer agent is used in an amount of from 0.05 to 5% by weight, based on in monomers.
    [0008]
    8. Polymer dispersion, containing starch, finely divided according to any one of the preceding claims, characterized by the fact that the chain transfer agent is a monocyclic monoterpene.
    [0009]
    9. Polymer dispersion, containing starch, finely divided according to any of the preceding claims, characterized by the fact that the polymerization is carried out in the presence of from 0.05 to 5% by weight of terpinolene as the chain transfer agent .
    [0010]
    10. Process for the preparation of polymer dispersions, containing starch, finely divided as defined in any one of claims 1 to 9, characterized in that (a) from 15 to 35% by weight of at least one optionally substituted styrene, (b) from more than 65 to 85% by weight of at least one C1-C12-alkyl acrylate and / or a C1-C12-alkyl methacrylate, (c) from 0 to 10% by weight of at least one other copolymerizable ethylenically unsaturated monomer, are used as ethylenically unsaturated monomers, the sum of (a) + (b) + (c) being 100% based on the active monomer content and (d) from 15 to 40% by weight of at least one degraded starch that has a Mw molar mass from 1000 to 65,000 g / mol, based on the total weight of the solids content of the components (a) + (b) + (c) + (d), are polymerized in the presence of a redox initiator in an aqueous medium and polymerization is carried out in the presence of at least 0.01% by weight, based on the monomers used , of at least one terpene-containing chain transfer agent, and wherein the polymer dispersion optionally comprises an aluminum compound.
    [0011]
    Process according to claim 10, characterized in that the chain transfer agent is a monocyclic monoterpene.
    [0012]
    Process according to claim 10 or claim 11, characterized in that the polymerization is carried out in the presence of from 0.05 to 5% by weight of at least one terpene-containing chain transfer agent.
    [0013]
    Process according to claim 12, characterized in that the polymerization is carried out in the presence of from 0.05 to 5% by weight of terpinolene as the chain transfer agent.
    [0014]
    Process according to any one of claims 10 to 13, characterized in that an initiator of the group consisting of hydrogen peroxide, peroxides, hydroperoxides and / or azo initiators is added to the polymer dispersion after the end of the main polymerization and post-polymerization is carried out.
    [0015]
    Process according to any one of the preceding claims, characterized in that tert-butyl hydroperoxide is added to the polymer dispersion for postpolymerization.
    [0016]
    16. Use of polymer dispersion, containing starch, finely divided as defined in claims 1 to 9, the use characterized by the fact that it is for a sizing agent for paper, cardboard and cardboard.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE3627594A1|1986-08-14|1988-02-18|Basf Ag|SIZING AGENT FOR PAPER BASED ON FINE-PARTED AQUEOUS DISPERSIONS|
    DE3702712A1|1987-01-30|1988-08-11|Basf Ag|SIZING AGENT FOR PAPER BASED ON FINE-PARTED AQUEOUS DISPERSIONS|
    EP0406461B1|1989-07-05|1994-01-05|Giulini Chemie GmbH|Paper sizing agent containing a cationic dispersant|
    DE19806745A1|1998-02-18|1999-08-19|Bayer Ag|Aqueous polymer dispersion useful as surface sizing agent for paper, cardboard etc.|
    JP2000239992A|1999-02-19|2000-09-05|Japan Pmc Corp|Surface sizing and production of coated paper|
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    DE102005030787A1|2005-06-29|2007-01-11|Basf Ag|Finely divided, starch-containing polymer dispersions|
    DE102005030789A1|2005-06-29|2007-01-11|Basf Ag|Finely divided, starch-containing polymer dispersions|
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    JP6760344B2|2018-09-18|2020-09-23|栗田工業株式会社|Surface sizing agent for papermaking|
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    FI20196021A1|2019-11-27|2021-05-28|Ch Polymers Oy|A polymer dispersion comprising hemicellulose|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-06-02| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-11-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161547081P| true| 2011-10-14|2011-10-14|
    US61/547081|2011-10-14|
    EP11185268.7|2011-10-14|
    EP11185268|2011-10-14|
    PCT/EP2012/070188|WO2013053840A2|2011-10-14|2012-10-11|Finely divided, starch-containing polymer dispersions, processes for their preparation and use as sizes in papermaking|
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