Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/14—Monomers containing only one unsaturated aliphatic radical
  • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
  • C08F216/1425—Monomers containing side chains of polyether groups
  • C08F216/1433—Monomers containing side chains of polyethylene oxide groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/14—Monomers containing only one unsaturated aliphatic radical
  • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
  • C08F216/1425—Monomers containing side chains of polyether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/14—Monomers containing only one unsaturated aliphatic radical
  • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
  • C08F216/1425—Monomers containing side chains of polyether groups
  • C08F216/1441—Monomers containing side chains of polypropylene oxide groups

Definitions

• the present invention relates to the use of reactive monomers as plasticizers in copolymers.
• the invention further relates to copolymers which by the
• the present invention relates to methods of lowering the glass transition temperature of copolymers using the reactive monomers. Further embodiments of the present invention are the claims, the
• JP2006160829 A2 describes the preparation of alkenyl polyethers which can serve as starting materials for emulsifiers in the emulsion polymerization.
• EP2457973 A1 describes the use of water-soluble, hydrophobically associating copolymers as additives in the development, exploitation and completion of underground oil and natural gas deposits.
• Such copolymers may contain monomers provided by alkoxylation of ethylenically unsaturated alcohols, such as hydroxybutyl vinyl ether, optionally followed by etherification.
• EP1069139 A2 describes the preparation of aqueous dispersions by polymerization of olefinically unsaturated, water-insoluble compounds in the presence of water-soluble allyl or vinyl ether macromonomers. Furthermore, the use of the macromonomers in emulsion or suspension polymerizations is described.
• copolymers which are prepared by free-radical copolymerization of at least one olefinically unsaturated polyoxyalkylene alcohol or polyester alcohol adduct and other monomers are described. These copolymers find use as auxiliaries and / or additives in formulations for the preparation of polyisocyanate polyaddition products.
• WO 03/062288 A1 describes the use of associating polymers which are soluble in an alkaline medium and which are HBVE or isoprenol associating monomers.
• DE10163258 A1 describes allyl polyalkylene glycol ether carboxylates and vinyl polyalkylene glycol ether carboxylates and their use as copolymerizable emulsifiers and hydrophilic monomers in emulsion polymerization.
• WO 99/61494 A1 describes the preparation of copolymers containing allylic monomers, for example allyl alcohols or alkoxylated allyl alcohols. The use of such copolymers as reactive plasticizers in thermoplastic polymers is described. However, no application example of such reactive plasticizers in specific thermoplastic polymers is disclosed in WO 99/61494 A1.
• the reactive comonomers used according to the invention have in particular the function of a plasticizer in the preparation of copolymers.
• Plasticizers are substances that are widely added to plastics, paints, varnishes, gums, adhesives and films to make them softer, more flexible, smoother and more elastic in use or further processing. They may be, for example, low-volatile esters, fatty oils, soft resins or camphor.
• the plasticizer is introduced in the course of a copolymerization.
• the plastic remains permanently soft and it does not come to a diffusing out of the plasticizer.
• vinyl chloride is polymerized with up to 20 percent vinyl acetate.
• Copolymerization of vinyl chloride are maleic acid, ethene, methyl vinyl ether or methyl acrylate.
• the present invention relates to the use of compounds of the general
• R, R 2 , R 3 independently of one another, identical or different, denote H or -CI-,
• R 4 is single bond, linear or branched C 1 -C 6 -alkylene
• R 5 , R 6 independently of one another, identical or different, denote H, C 1 -C 5 -alkyl or aryl,
• R 7 are independently, the same or different, H or, Ci-C6-alkyl, and n integer from 0 to 200, as plasticizers in copolymers.
• the [-CHR 5 -CHR 6 -O-] n unit of the general formula (I) may according to the invention have block structure and / or a random composition, which are preferably propylene oxide (PO) units.
• the units [-CHR 5 -CHR 6 -O-] n of formula (I) may or may not be identical. For example, it is also possible that this is a homogeneous PO or ethylene oxide (EO) chain with n PO or
• EO units or that this is a heterogeneous ethylene oxide / propylene oxide (EO / PO) chain with n (EO + PO) units, wherein the EO / PO distribution can be block, alternating or random.
• the units [-CHR 5 -CHR 6 -O-] n of the formula (I) are identical, for example PO.
• the compounds of the general formula (I) can be used according to the invention in principle as plasticizers in copolymers which are prepared in free-radical, anionic and cationic polymerization, preferably in the free-radical.
• the corresponding polymerization reaction can be carried out according to the invention in emulsion, in solution or in bulk, for example in emulsion.
• compounds of formula (I) are used as plasticizers in copolymers prepared in a free radical emulsion polymerization reaction.
• a further advantage of the use according to the invention of compounds of the general formula (I) is that they can reduce the viscosity of the polymer dispersion as described here and shown by way of example. This makes it possible, for example, to prepare dispersions of higher solids content. As a result, logistics costs (packaging, transport) can be saved because the products contain less water and more active substance. So far, this was limited because of the increasing viscosity with increasing solids content.
• polymerization or specific polymerizations such as “emulsion polymerization” are also used when two or more different monomers are used and therefore in the context of the present invention also include copolymerization or emulsion copolymerization.
• the compounds to be used in accordance with the invention have a softening effect on copolymers prepared therewith by lowering the glass transition temperature of the copolymers as described herein and shown in the examples.
• An advantage of the use according to the invention is that the compounds used are non-volatile and readily biodegradable. In addition, they have no or only a very small diffusion from the copolymer.
• both R 1 , R 2 and R 3 are H. In another embodiment, R 1 and R 2 are H and R 3 is -CH 3 .
• X is O. In another embodiment, X is C2-alkoxyl.
• R 4 is a linear C 4 alkylene (butyl). In another embodiment, R 4 is a single bond.
• R 5 or R 6 is H, but not R 5 and R 6 are H.
• R 5 or R 6 is -CH 3.
• R 5 or R 6 is H and the other radical R 5 or R 6 is -CH 3.
• R 5 may be H and R 6 is -CH 3.
• R 7 is H.
• n can be any number> 1, for example a number between 4 and 21, between 5 and 20, between 7 and 17, or between 8 and 12.
• n 10.
• both R 1 , R 2 and R 3 are H, X is O, R 4 is linear C 4 alkylene (butyl), R 5 is H, R 6 is -CH 3 , and is R 7 H.
• the compound of formula (I) is a hydroxybutyl vinyl ether.
• R 1 and R 2 are identical to each other particular embodiment of the present invention.
• R 3 is -CH 3
• X is C 2 alkoxyl
• R 4 is a single bond, ie a isoprenol derivative.
• the compound of formula (I) to be used according to the invention can have an OH number of 2 mg KOH / g to 225 mg KOH / g, preferably 10 mg KOH / g to 225 mg KOH / g, preferably 20 mg KOH / g to 225 mg KOH / g, more preferably 50 mg KOH / g to 120 mg KOH / g.
• the OH number can be determined in this case by methods known to the person skilled in the art, e.g. according to DIN 53240 (wet number) or, preferably, by TAI-NMR as known to those skilled in the art and described here by way of example.
• the polydispersity of the compound of formula (I) to be used according to the invention can be any polydispersity of the compound of formula (I) to be used according to the invention.
• polydispersity can in this case be determined by methods known to the person skilled in the art, preferably by GPC as known to the person skilled in the art and described here by way of example.
• the compound of the formula (I) can be copolymerized according to the invention, for example, with one or more olefinically unsaturated compounds (comonomers).
• compounds (comonomers) can be used selected from the group consisting of vinyl-aromatic compounds, ethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms, Ci-Cio-alkyl esters of ethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms , Vinyl acetate, ethene, propene, 1,3-butadiene, isoprene, and ⁇ -olefins having 10 to 250 carbon atoms, each in pure form or as an isomer mixture.
• further possible compounds (comonoemers) in this context may also be SO 4 -containing monomers such as, for example, arylamidopropanesulfonic acid and / or PO 4 -containing monomers such as, for example, vinylphosphonic acid.
• SO 4 -containing monomers such as, for example, arylamidopropanesulfonic acid and / or PO 4 -containing monomers such as, for example, vinylphosphonic acid.
• one or more of the comonomers are copolymerized with the compound of formula (I).
• Methods for copolymerization are known in the art and include, inter alia, radical copolymerization, for example. Emulsion polymerization. As already shown and as further shown herein, it is by the invention
• the term "plasticizer” or "softening effect” is understood to mean the ability to lower the glass transition temperature of a copolymer containing the compound of the formula (I).
• the term "plasticizer” or "softening effect” is understood to mean the ability to lower the glass transition temperature of a copolymer containing the compound of the formula (I).
• the degree of lowering of the glass transition temperature depends on the glass transition temperature of the other comonomers used and the amount of comonomer of formula (I) used. The lower the glass transition temperature (of the corresponding homopolymer) of a comonomer used, the stronger the lowering of the glass transition temperature.
• the glass transition temperature of the copolymer is lowered more as the more of the low glass transition temperature comonomer is used.
• the glass transition temperature is measured by differential scanning calorimetry (DSC) as also exemplified herein.
• DSC differential scanning calorimetry
• the present invention further provides methods for lowering the glass transition temperature. All mentioned definitions and descriptions regarding the inventive use of the compounds according to
• formula (I) likewise relates to the process for lowering the glass transition temperature by means of the compounds of the formula (I) and vice versa, as will be readily apparent to one skilled in the art.
• Such a process is a copolymerization and known to the skilled person. It can be carried out, for example, as follows. First, monomers which are relatively higher
• the resulting copolymer will according to the invention have a lower glass transition temperature than the homo- or copolymer of the corresponding monomers without a compound of formula (I).
• the glass transition temperature of the copolymers will be between the corresponding values of the individual monomers.
• an effective amount of from 0.1 to 50, preferably from 0.5 to 30, preferably from 1 to 20, particularly preferably from 1 to 10,% by weight of a compound of the formula (I) is used in the polymerization. added, based on the total mass of monomers used. As a result, a reduction of the invention
• Glass transition temperature of the copolymer effected preferably by 5 to 70 K.
• copolymers according to the invention can be prepared by processes known to those skilled in the art, for example by free-radical copolymerization.
• the free-radical co-polymerization can be carried out in aqueous or organic solvents or their
• Copolymers take place. A preparation via solvent-free co-polymerization is possible.
• the radical emulsion polymerization can be used.
• comonomers for example, one or more olefinically unsaturated compounds (comonomers) can be used.
• compounds (comonomers) can be used selected from the group consisting of vinyl-aromatic compounds, ethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms, Ci-Cio-alkyl esters of ethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms , ethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms, vinyl acetate, ethene, propene, 1, 3-butadiene, isoprene, and ⁇ -olefins having 10 to 250 carbon atoms, in each case in pure form or as an isomer mixture.
• compounds (comonomers) in this context may also be SC-containing monomers such as, for example, arylamidopropanesulfonic acid and / or PC-containing monomers such as, for example, vinylphosphonic acid.
• SC-containing monomers such as, for example, arylamidopropanesulfonic acid and / or PC-containing monomers such as, for example, vinylphosphonic acid.
• PC-containing monomers such as, for example, vinylphosphonic acid.
• one or more of the comonomers can be copolymerized with the compound of the formula (I).
• the present invention also encompasses the preparation of copolymers using compounds of formula (I).
• compounds of formula (I) for example, from 0.1 to 50, preferably from 0.5 to 30, preferably from 1 to 20, particularly preferably from 1 to 10,% by weight of the compound as defined in one of claims 1 to 10 are used, based on the
• a free-radical polymerization is carried out here, for example a free-radical emulsion polymerization.
• comonomers for example, one or more olefinically unsaturated compounds (comonomers) can be used.
• compounds (comonomers) can be used selected from the group consisting of vinyl aromatic compounds, ethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms, Ci-Cio-alkyl esters of ethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms , Vinyl acetate, ethene, propene, 1, 3-butadiene, isoprene, and ⁇ -olefins having 10 to 250 carbon atoms, each in pure form or as an isomer mixture.
• Other possible compounds (comonoemers) according to the invention in this context also SC-containing
• Monomers such as Arylamidopropansulfonklare and / or PC-containing monomers such as, for example, be vinylphosphonic.
• one or more of the comonomers are copolymerized with the compound of formula (I).
• the present invention further encompasses copolymers which are prepared by the process according to the invention shown and described here or by the process according to the invention
• these copolymers contain from 0.1 to 50, preferably 0.5 to 30, preferably 1 to 20, particularly preferably 1 to 10% by weight of the compound as defined in any one of claims 1 to 10, based on the total mass of monomers.
• copolymers prepared by emulsion polymerization can be used, for example, as binders in paints and varnishes or as pressure-sensitive adhesives.
• Other copolymers of the invention can also be used as components of rubbers and polymeric materials.
• the comonomers to be used according to the invention also have an influence on the viscosity of the polymer dispersion. As shown in the examples, the use of the comonomers to be used according to the invention in specific formulations also leads to a reduction in the dispersion viscosity. This offers the
• the compounds of formula (I) can be prepared by the skilled person known manner, for example by alkoxylation of unsaturated alcohols (such as, but not limited to, hydroxybutyl vinyl ether or isoprenol). Such a method is known to the person skilled in the art and described, for example, in DE 10 2007 057 927 A1.
• HBVE hydroxybutyl vinyl ether
• K-methylate 32% in methanol
• the metering of propylene oxide (PO) was started and metered in so that a total pressure of 1.4 bar was not exceeded.
• the first amount of PO (830 kg, 14.39 kmol, 3 mol equivalent based on HBVE) was metered in and left to react for a further 2 hours. It was then cooled to 75 ° C and simultaneously relaxed. Then another 57 kg of K-methylate (32% in methanol) - corresponds to 1.29% by weight (based on the batch) was added.
• the reactor was evacuated to ⁇ 100 mbar and heated to 140 ° C. Meanwhile, about 39 kg of methanol were distilled off in about 1 h. The vacuum was released with nitrogen and an overpressure of 0.05 bar was set. Thereafter, the dosage of propylene oxide (PO) was restarted using a
• Filtered filter suction filter There were a total of 3850g delivered.
• UV detector L4000 (254 nm), Merck GmbH, 64239 Darmstadt
• Both sets are in tempering furnaces at 30 ° C
• the anhydrous sample (content ⁇ 1%) is dissolved 1% in internal standard solution, possibly filtered and sprayed onto the separation columns via an autosampler. Is evaluated
• Apparatus 1.7 liter reaction vessel made of glass, which is equipped with an anchor stirrer and immersed in a water bath for temperature control.
• two supply vessels for the feeds one stirred for the monomer premix and one not stirred for the initiator solution).
• the feed vessels are attached to a weigh module with which the metered quantity can be determined exactly.
• the metered addition takes place by means of a slight overpressure in the feed vessel, controlled by compressed air valves.
• Internal reactor temperature, water bath temperature and feeds are controlled by a computer program.
• Comonomer system styrene, n-butyl acrylate (alternatively HBVE + 10 PO (according to Example 1.2)) methacrylic acid (Screening 1, Karolina)
• the reaction vessel was filled with a solution of 4 g of potassium peroxodisulfate (K 2 S 2 O 8) in 250 g of deionized water, and from the feed vessel, 225 g of the preemulsion were metered in. This mixture was heated to 60 ° C and after reaching the temperature 8 g of initiator solution from the feed vessel 2 are metered. After stirring for 5 minutes 60 ° C began the parallel dosing of the pre-emulsion from feed vessel 1 and the initiator from feed vessel 2. The pre-emulsion was added over a period of 150 min, the initiator over a period of 160 min. During the entire metering time, the internal temperature was kept at 60 ° C. After completion of the Initiatorzulaufs the internal temperature was raised to 65 ° C and held there for 60 min. For additional
• the dispersion was cooled to room temperature and adjusted to a pH of 7-8 with 25% aqueous ammonia solution.
• the dispersion was filled into containers via a 150 micron filter.
• Apparatus 1.7 liter glass reaction vessel equipped with an anchor stirrer and immersed in a water bath for temperature control.
• two supply vessels for the feeds one stirred for the monomer premix and one not stirred for the initiator solution).
• the feed vessels hung on a weigh module, with which the metered quantity can be determined exactly.
• the metered addition was carried out by means of a slight overpressure in the feed vessel, controlled by compressed air valves. Internal reactor temperature, water bath temperature and feeds were controlled by a computer program.
• Styrene (A g), n-butyl acrylate (B g) (alternatively HBVE + 10 PO (according to Example 1 .2) C g), methacrylic acid (15 g), deionized water (450 g) and anionic emulsifier (Disponil®
• FES 77 from BASF SE - aqueous solution of a C12C14 fatty alcohol ether sulfate with 30 EO - corresponding to 20 g of active substance) were mixed and added to the stirred feed vessel 1.
• the reaction vessel was filled with a solution of 4 g of potassium peroxodisulfate (K 2 S 2 O 8) in 250 g of deionized water and 225 g of the preemulsion were metered from the feed vessel. This mixture was heated to 60 ° C and after reaching the temperature 8 g of initiator solution from the feed vessel 2 were added. After stirring for 5 minutes at 60 ° C, the parallel dosing of the preemulsion from feed vessel 1 and the initiator from feed vessel 2 began. The preemulsion was metered in over a period of 150 minutes, the initiator over a period of 160 minutes. During the entire metering time, the internal temperature was kept at 60 ° C. After completion of the Initiatorzulaufs the internal temperature was raised to 65 ° C and held there for 60 min.
• K 2 S 2 O 8 potassium peroxodisulfate
• the dispersion was filled into containers via an 80 micron filter.
• the dry content of the dispersion was determined by drying about 5 g in a
• Particle size The particle size was determined by laser diffraction in a Beckman Coulter LS 13320 Diffraction Particle Size Analyzer The dso value determined by the instrument was expressed as the particle size (in nm).
• Viscosity Dynamic viscosity was determined using a Brookfield DV-II + RV spindle set (spindle 1) viscometer and reported in [mPas].
• Apparatus 1.7 liter glass reaction vessel equipped with an anchor stirrer and immersed in a water bath for temperature control.
• two supply vessels for the feeds one stirred for the monomer premix and one not stirred for the initiator solution).
• the feed vessels hung on a weigh module, with which the metered quantity could be determined exactly.
• the metered addition was carried out by means of a slight overpressure in the feed vessel, controlled by compressed air valves. Internal reactor temperature, water bath temperature and feeds were controlled by a computer program.
• Comonomer System vinyl acetate, VeoVA 10 ® from Momentive Specialty Chemicals Inc. (alternatively HBVE + 10 PO (described in Example 1 .2)) acrylic acid (Screening 4, Carolina)
• the reaction vessel was treated with a solution of 0.8 g potassium peroxodisulfate (K 2 S 2 O 8), 0.4 g disodium tetraborate (Na 2 B 4 07) and anionic emulsifier (Disponil® FES 32 from BASF SE - aqueous solution of a C12C14 fatty alcohol ether sulfate with 4 EO - corresponding to 2, 6 g of active substance) in a total of 395 g of deionized water.
• This mixture was heated to 80 ° C and after reaching the temperature, the parallel metering of the pre-emulsion from feed vessel 1 and the initiator from feed vessel 2 was started.
• K 2 S 2 O 8 potassium peroxodisulfate
• Na 2 B 4 07 disodium tetraborate
• anionic emulsifier Disonil® FES 32 from BASF SE - aqueous solution of a C12C14 fatty alcohol ether sulfate with 4 EO
• Preemulsion was added over a period of 180 min, the initiator over a period of 190 min. During the entire dosing time, the internal temperature is maintained at 80 ° C. After completion of the Initiatorzulaufs the internal temperature was maintained for a further 60 minutes with stirring at 80 ° C. For additional stabilization of the dispersion, within this post-reaction phase - after about 30 minutes - 27 g of a C16C18-
• the dispersion was filled into containers via a 150 micron filter.
• the glass transition temperature was determined by means of Dynamic Scanning Calorimetry (DSC). For this purpose, the dispersion was poured out and filmed overnight, then dried at 120 ° C for 1 h in vacuo. About 9 mg were measured which were cooled rapidly from 150 ° C before the actual measurement. The subsequent measurement was at a
• Apparatus 1.7 liter reaction vessel made of glass, which is equipped with an anchor stirrer.
• the temperature control was carried out via the double jacket of the vessel by means of a thermostat.
• two supply vessels for the feeds one stirred for the monomer premix and one not stirred for the initiator solution).
• the feed vessels were attached to a weighing module with which the metered quantity could be determined exactly.
• the metered addition was carried out by means of a slight overpressure in the feed vessel, controlled by compressed air valves. Internal reactor temperature, water bath temperature and feeds were controlled by a computer program.
• Comonomer system methyl methacrylate, 2-ethylhexyl acrylate (alternatively HBVE + 10 PO (according to Example 1 .2)), methacrylic acid Procedure: Preparation of the comonomer premix:
• Methyl methacrylate (A g), 2-ethylhexyl acrylate (Bg), HBVE + 10 PO (according to Example 1 .2) C g, methacrylic acid (15 g), deionized water (268.44 g) and anionic emulsifier (Disponil® FES 32 from BASF SE - aqueous solution of a C12C14 fatty alcohol ether sulfate with 4 EO - corresponding to 5 g of active substance) were mixed and added to the stirred feed vessel
• the reaction vessel was treated with a solution of 0.4 g of potassium peroxodisulfate (K 2 S 2 O 8), 0.8 g of sodium bicarbonate (NaHCO 3) and 36.42 g of anionic emulsifier (Disponil.RTM
• FES 32 from BASF SE - aqueous solution of a C12C14 fatty alcohol ether sulfate with 4 EO - corresponding to 1 1 g of active ingredient) in 405 g of deionized water.
• the preemulsion was metered in over a period of 80 minutes, the initiator over a period of 90 minutes. During the entire dosing time, the
• the dispersion was filled into containers via an 80 micron filter.
• the coagulum collected in the filter was washed with deionized water and dried at 50 ° C. for 24 h. It was weighed together with the coagulum scraped off by stirrer and thermometer, which was blotted dry in a cloth. The amount of coagulum was expressed as% of the total theoretical solids content.
• the dry content of the dispersion was determined by drying about 5 g in a "Mettler Toledo Halogen Moisture Analyzer HR 83" at 150 ° C. for 20 min The quotients from the determined dry content and the theoretical dry content were calculated as the conversion (in%). ).
• Particle size The particle size was determined by laser diffraction in a Beckman Coulter LS 13320 Diffraction Particle Size Analyzer The dso value determined by the instrument was expressed as the particle size (in nm).
• Viscosity The dynamic viscosity was measured at room temperature with a Brookfield DV
• the sample / dispersion to be examined was poured out and dried overnight at room temperature. Approximately 6-9 mg of the dried sample was used for the measurement. Before the measurement, the sample was heated to temperatures of 120 ° C - 150 ° C and cooled rapidly. Thereafter, the sample was heated at a heating / cooling rate of
• the device used was a DSC Q2000 from TA Instruments.

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