DE102007011427A1 - Use of proton-delivering and / or proton-accepting polymer particles - Google Patents

Abstract

The present invention relates to the use of emulsion polymerized polymer particles having an average particle diameter in the range of 5 to 500 nm, containing surface and / or non-surface ionogenic groups, as proton-providing and / or proton-accepting substance in heterogeneous chemical processes, particularly suitable polymer particles for the use in such processes as well as composite materials and moldings containing them.

Description

The The present invention relates to the use of by emulsion polymerization produced polymer particles having an average particle diameter in the range of 5 to 500 nm, containing surface and / or non-surface-active ionogenic groups, as proton-delivering and / or proton-accepting substance in heterogeneous chemical processes, particularly suitable polymer particles for use in such processes as well as containing them Composite materials and shaped bodies.

For many heterogeneous methods, d. H. such processes in which at least is a phase boundary, become immobilized, insoluble Proton donors or proton donors or proton acceptors needed. The use of immobilized proton donors or proton donors or proton acceptors offers fundamental advantages, like a facilitated separation.

For Such methods generally have the need for new proton suppliers or proton acceptors with a new or modified property profile.

The use of microgels for property control of elastomers or thermoplastics is known ( WO2005 / 033185 ). In some cases, microgels have also been used which have functional groups on the surface or over the entire cross section.

Not So far, the use of proton-delivering or has been known proton accepting groups modified polymer particles in Nano size range in heterogeneous chemical processes, the one immobilized proton donor or proton acceptor require.

The The present invention relates to the use of by emulsion polymerization produced polymer particles having an average particle diameter in the range of 5 to 500 nm, containing ionogenic groups as proton-donating and / or proton-accepting substance, in heterogeneous chemical Processes are included according to the invention also applications in which the polymer particles at least initially partially neutralized.

Of the Use of said polymer particles offers over classic Proton donors or proton acceptors numerous advantages, since the chemical and physical properties of polymer particles, such as Particle size, particle morphology, swelling behavior, Catalytic activity, hardness, dimensional stability, Tackiness, aging resistance, impact resistance on the one hand by the manufacturing process, in particular by the polymerization process, as well as by selecting suitable base monomers and on the other hand Selection of suitable ionogenic groups their concentration and settlement area in the polymer particles within wide limits targeted or customized can be. Heterogeneous processes or processes are those in which phase boundaries, in particular solid / liquid and / or solid / gaseous, wherein the polymer particles naturally attributable to the solid phase. proton-donating or proton-accepting means according to the invention in particular, that the polymer particles release protons to a surrounding medium can or can record. In a matrix, especially in a polymer matrix, the polymer particles are capable give the matrix a proton conductivity.

For the purposes of the invention, emulsion polymerization is understood in particular to be a process known per se in which water is used as the reaction medium, in which the monomers used are polymerized in the presence of emulsifiers and free-radical-forming substances to form aqueous polymer latices (see below) Römpp Lexikon der Chemie, Volume 2, 10th Edition 1997; PA Lovell, MS EI-Aasser, Emulsion Polymerization and Emulsion Polymers, John Wiley & Sons, ISBN: 0 471 96746 7; H. Gerrens, Fortschr. Hochpolym. Research 1, 234 (1959) ). In contrast to suspension or dispersion polymerization, the emulsion polymerization generally gives finer particles which allow a lower particle spacing in a matrix. The smaller particles are with their small mean diameter below the critical defect size, ie the matrices containing them are subject to only minor mechanical impairments, with a corresponding degree of dispersion. Particles of size less than 500 nm are generally not accessible by suspension or dispersion polymerization, which is why these particles are generally unsuitable for the purposes of this patent application.

The choice of monomers sets the glass transition temperature and the glass transition width of the polymer particles. The determination of the glass transition temperature (Tg) and the width of the glass transition (ΔTg) of the microgels is carried out by differential scanning calorimetry (DSC), preferably as described below. For this purpose, two cooling / heating cycles are carried out for the determination of Tg and ΔTg. Tg and ΔTg who determined in the second heating cycle. For the determinations, approximately 10-12 mg of the selected microgel is placed in a Perkin-Elmer DSC sample container (standard aluminum pan). The first DSC cycle is carried out by first cooling the sample to -100 ° C with liquid nitrogen and then heating to + 150 ° C at a rate of 20K / min. The second DSC cycle is started by immediately cooling the sample as soon as a sample temperature of + 150 ° C is reached. The cooling takes place at a speed of about 320 K / min. in the second heating cycle, the sample is again heated to + 150 ° C as in the first cycle. The heating rate in the second cycle is again 20K / min. Tg and ΔTg are determined graphically on the DSC curve of the second heating process. For this purpose, three straight lines are applied to the DSC curve. The 1st straight line is applied to the curve part of the DSC curve below Tg, the 2nd straight line to the curve branch with inflection point passing through Tg and the 3rd straight line to the curve branch of the DSC curve above Tg. In this way, three straight lines with two intersections are obtained. Both intersections are each characterized by a characteristic temperature. The glass transition temperature Tg is obtained as the mean value of these two temperatures and the width of the glass transition ΔTg is obtained from the difference between the two temperatures.

rubbery Polymer particles have a glass transition temperature of generally <23 ° C. Thermoplastic polymer particles generally have a glass transition temperature a glass transition temperature of> 23 ° C.

The Width of the glass transition is used in the invention Polymer particles preferably greater than 5 ° C, more preferably greater than 10 ° C.

rubbery Polymer particles are preferably those based on conjugated Such as butadiene, isoprene, 2-chlorobutadiene and 2,3-dichlorobutadiene, and ethene, esters of acrylic and methacrylic acid, vinyl acetate, Styrene or derivatives thereof, acrylonitrile, acrylamides, methacrylamides, Tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, double bond-containing Hydroxy compounds such. B. hydroxyethyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acrylate, hydroxybutyl methacrylate, acrolein or combinations from that.

preferred Monomeric or monomer combinations include; butadiene, Isoprene, acrylonitrile, styrene, alpha-methylstyrene, chloroprene, 2,3-dichlorobutadiene, Butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, tetrafluoroethylene, Vinylidene fluoride and hexafluoropropene.

"On Base "here means that the polymer particles are preferred to more as 60% by weight, preferably more than 70% by weight, more preferably more consist of 90% by weight of said monomers.

The Polymer particles may be crosslinked or uncrosslinked. in the Traps of crosslinked polymer particles are also called microgels. The polymer particles can be especially based on of homopolymers or random copolymers. The terms Homopolymers and random copolymers are known in the art and, for example, by Vollmert, Polymer Chemistry, Springer 1973.

BR:

Polybutadien,

ABR;

Butadien/Acrylsäure-C1-4Alkylestercopolymere,

IR:

Polyisopren,

SBR:

statistische Styrol-Butadien-Copolymerisate mit Styrolgehalten von 1–60, vorzugsweise 5–50 Gewichtsprozent,

FKM:

Fluorkautschuk,

ACM:

Acrylatkautschuk,

NBR:

Polybutadien-Acrylnitril-Copolymerisate mit Acrylnitrilgehalten von 5–60, vorzugsweise 10–60 Gewichtsprozent,

CR:

Polychloropren

EAM:

Ethylen/Acrylatcopolymere,

EVM:

Ethylen/Vinylacetatcopolymere.

As the polymer base of the rubbery, crosslinked or uncrosslinked polymer particles containing ionic groups, may be used in particular;

BR:

polybutadiene,

ABR;

Butadiene / acrylic acid C1-4Alkylestercopolymere,

IR:

polyisoprene,

SBR:

styrene-butadiene random copolymers having styrene contents of 1-60, preferably 5-50 weight percent,

FKM:

Fluoro rubber,

ACM:

acrylate,

NBR:

Polybutadiene-acrylonitrile copolymers having acrylonitrile contents of 5-60, preferably 10-60, weight percent,

CR:

polychloroprene

EAM:

Ethylene / acrylate copolymers,

EVM:

Ethylene / vinyl acetate copolymers.

Inventive non-rubbery, in particular thermoplastic polymer particles expediently have a glass transition temperature Tg of more than 23 ° C. The width of the glass transition in the thermoplastic polymer particles is preferably greater than 5 ° C (the Tg or the width of the glass transition is determined as described above). Non-rubbery, in particular thermoplastic polymer Particles are preferably those based on methacrylates, in particular methyl methacrylate, styrene or styrene derivatives, such as alpha-methylstyrene, para-methylstyrene, acrylonitrile, methacrylonitrile, vinylcarbazole or combinations thereof. "On the basis" here means that the polymer particles preferably consist of more than 60% by weight, preferably more than 70% by weight, more preferably more than 90% by weight, of the stated monomers.

More preferred thermoplastic polymer particles are those based on methacrylates, especially methyl methacrylate, styrene, alpha-methylstyrene and acrylonitrile, The polymer particles preferably have an approximately spherical Geometry on.

The polymer particles used according to the invention have an average particle diameter in the range from 5 to 500 nm, preferably from 20 to 400, particularly preferably from 30 to 300 nm. The average particle diameter is determined by ultracentrifugation with the aqueous latex of the polymer particles from the emulsion polymerization. The method gives an average value for the particle diameter taking into account any agglomerates. ( HG Müller (1996) Colloid Polymer Science 267: 1113-1116 and W. Scholtan, H. Lange (1972) Kolloid-Z u. Z. Polymers 250: 782 ). Ultracentrifugation has the advantage of characterizing the total particle size distribution and calculating various means such as number average and weight average from the distribution curve.

The Mean diameter data used according to the invention refer to the weight average.

In the following, diameter data such as d ₁₀ , d ₅₀ and d ₈₀ are used. These data indicate that 10, 50 or 80% by weight of the particles have a diameter which is smaller than the corresponding numerical value in% by weight.

The Diameter determination by means of dynamic light scattering leads in a first approximation to comparable average particle diameters. It is also done on the latex. Common are lasers that are at 633 nm (red) and at 532 nm (green) work. When the dynamic light scattering is not like the Ultracentrifugation the entire particle size distribution characterized, but you get an average, at the large particle disproportionately weighted become.

The have polymer particles used in the invention preferably has a weight-average particle diameter in the range from 5 to 500 nm, preferably from 20 to 400, more preferably from 30 to 300 nm.

The Particles are prepared by emulsion polymerization, wherein by varying the starting materials such as emulsifier concentration, initiator concentration, Liquor ratio of organic to aqueous Phase, ratio of hydrophilic to hydrophobic monomers, Amount of crosslinking monomer, polymerization temperature, etc. the Particle size in a wide diameter range is set.

To the polymerization of the latices by vacuum distillation or treated by treatment with superheated steam, in particular unreacted volatile components Separate monomers.

The work-up of the polymer particles produced in this way can be carried out, for example, by evaporation, electrolytic coagulation, by co-coagulation with another latex polymer, by freeze coagulation (cf. U.S. Patent 2,187,146 ) or by spray drying. In the workup by spray drying and commercial flow aids such as CaCO ₃ or silica can be added.

The used by emulsion polymerization according to the invention produced polymer particles are in a preferred embodiment at least partially networked.

The crosslinking of the polymer particles produced by emulsion polymerization is preferably carried out by the addition of polyfunctional monomers in the polymerization, such as. B. by the addition of compounds having at least two, preferably 2 to 4 copolymerizable C = C double bonds, such as diisopropenylbenzene, divinylbenzene, divinyl ether, divinylsulfone, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, N, N'-m Phenylene maleimide, 2,4-toluylenebis (maleimide), triallyl trimellitate, acrylates and methacrylates of polyhydric, preferably 2- to 4-valent C 2 to C 10 alcohols, such as ethylene glycol, 1,2-propanediol, butanediol, hexanediol, polyethylene glycol with 2 to 20, preferably 2 to 8 oxyethylene units, neopentyl glycol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol, sorbitol and unsaturated polyes from aliphatic di- and polyols and maleic acid, fumaric acid, and / or itaconic acid.

The Crosslinking of the polymer particles can be done directly during the Emulsion polymerization, such as by copolymerization with crosslinking acting multifunctional compounds or by subsequent Crosslinking can be achieved as described below. The direct Crosslinking during the emulsion polymerization is preferred. Preferred multifunctional comonomers are compounds having at least two, preferably 2 to 4 copolymerizable C = C double bonds, such as diisopropenylbenzene, divinylbenzene, divinyl ether, divinylsulfone, diallyl phthalate, Triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, N, N'-m-phenylene maleimide, 2,4-toluylenebis (maleimide) and / or triallyl trimellitate. About that In addition, the acrylates and methacrylates of polyvalent, preferably 2- to 4-valent C 2 to C 10 alcohols, such as ethylene glycol, Propandiol-1,2, butanediol, hexanediol, polyethylene glycol with 2 to 20, preferably 2 to 8 oxyethylene units, neopentyl glycol, bisphenol A, Glycerol, trimethylolpropane, pentaerythritol, sorbitol with unsaturated Polyesters of aliphatic di- and polyols as well as maleic acid, Fumaric acid, and / or itaconic acid.

The Crosslinking during emulsion polymerization may also be by continuing the polymerization up to high conversions or in the monomer feed process by polymerization with high internal Sales are made. Another possibility exists also in the execution of the emulsion polymerization in the absence of regulators.

For the crosslinking of the uncrosslinked or the weakly crosslinked polymer particles Following the emulsion polymerization is set on the latices obtained in the emulsion polymerization are best become.

suitable Crosslinking chemicals are, for example, organic peroxides, such as dicumyl peroxide, t-butyl cumyl peroxide, bis (t-butyl-peroxy-isopropyl) benzene, Di-t-butyl peroxide, 2,5-ditmethylhexane-2,5-dihydroperoxide, 2,5-dimethylhexine-3,2,5-dihydroperoxide, Dibenzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, t-butyl perbenzoate and organic azo compounds such as azo-bis-isobutyronitrile and Azo-bis-cyclohexanenitrile and di- and polymercapto compounds, such as dimercaptoethane, 1,6-dimercaptohexane, 1,3,5-trimercaptotriazine and mercapto-terminated polysulfide rubbers such as mercapto-terminated Reaction products of bis-chloroethylformal with sodium polysulfide.

The optimum temperature for carrying out the postcrosslinking is of course dependent on the reactivity of the crosslinker and can be carried out at temperatures from room temperature to about 180 ° C., optionally under elevated pressure (see Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/2, page 848 ). Particularly preferred crosslinking agents are peroxides.

The crosslinking of rubbers containing C =C double bonds into microgels can also be carried out in dispersion or emulsion with simultaneous, partial, possibly complete, hydrogenation of the C =C double bond by hydrazine as in US 5,302,696 or US 5,442,009 described or possibly other hydrogenating agents, for example Organometallhydridkomplexe done.

In front, During or after postcrosslinking, an increase in particle size may be necessary be carried out by agglomeration.

The Crosslinked polymer particles used according to the invention have expediently insoluble in toluene at 23 ° C. Proportions (gel content) of at least about 70% by weight, more preferably at least about 80% by weight, more preferably at least about 90% by weight. The toluene-insoluble fraction is thereby added in toluene 23 ° determined. This will be 250 mg of the polymer particles in 25 ml of toluene for 24 hours with shaking at 23 ° C. After centrifugation at 20,000 rpm, the insoluble Part separated and dried. The gel content results from the quotient of the dried residue and the weight and is expressed in weight percent.

The crosslinked polymer particles used in accordance with the invention furthermore advantageously have a swelling index in toluene at 23 ° C. of less than about 80, more preferably less than 60, more preferably less than 40. Thus, the swelling indices of the polymer particles (Qi) may more preferably be between 1-15 and 1-10. The swelling index is calculated from the weight of the solvent-containing polymer particles swollen in toluene at 23 ° for 24 hours (after centrifugation at 20,000 rpm) and the weight of the dry polymer particles: Qi = wet weight of the polymer particles / dry weight of the polymer particles.

to Determination of the swelling index is 250 mg the polymer particles in 25 ml of toluene with shaking for 24 h sources. The gel is centrifuged off and weighed and then dried at 70 ° C to constant weight and again weighed.

The contain polymer particles used in the invention ionogenic groups. According to the invention, ionogenic groups are those Group which are ionic or capable of forming ionic groups are. They are thus able to provide protons and / or to be proton accepting.

In a preferred embodiment, the ionic groups are selected from one or more of the following functional groups: -COOH, -SO ₃ H, -OSO ₃ H, -P (O) (OH) ₂ , -OP (OH) 2 and -OP (O) (OH) ₂ and / or their salts and / or derivatives thereof, in particular partial esters thereof. The salts represent the conjugate bases to the acidic functional groups, ie -COO ^- , -SO ₃ ^- , -OSO ₃ ^- , -P (O) ₂ (OH) ^- or -P (O) ₃ 3 ^- , -OP (O) ₂ 2 and -OP (O) ₂ (OH) ^- or -OP (O) ₃ 2 ^- in the form of their metal, preferably alkali metal or ammonium salts.

According to the invention particularly preferred ionic groups in the context of the invention are selected from -SO ₃ H, -PO (OH) ₂ , -OP (O) (OH) ₂ and / or their salts and / or derivatives thereof, in particular partial esters thereof.

The ionogenic groups can surface depending on the method of preparation and / or non-surface-active.

The ionogenic groups can be prepared by copolymerization accordingly functionalized monomers and / or by modification according to the Polymerization are introduced into the polymer particles.

functionalized For example, monomers are selected from the group consisting of which consists of: acrylic acid, methacrylic acid, vinylbenzoic acid, Itaconic acid, maleic acid, fumaric acid, Crotonic acid, vinylsulfonic acid, styrenesulfonic acid, Phosphonic acid or phosphoric acid group-containing Monomers with polymerizable C = C double bonds, such as vinylphosphonic acid, 2-phosphonomethylacrylic acid and 2-phosphonomethylacrylamide, Phosphonic acid or phosphoric acid esters of hydroxy-functional, polymerizable C = C double bond-containing monomers or Salts or derivatives thereof.

worin R eine zweiwertige organische Gruppe, wie insbesondere C1 bis C10-Alkylen ist. Bevorzugt ist R eine C2-C4 Alkylengruppe (d. h., eine C2-C4-Alkandiylgruppe), wie Methylen, Ethylen oder n-Propylen. Auch Salze dieser Verbindungen sind anwendbar, wie insbesondere Alkalimetallsalze bevorzugt das Natriumsalz oder Ammoniumsalze. Auch die entsprechenden Acrylate sind einsetzbar. Weiterhin können Partialester mit anderen gesättigten oder ungesättigten Carbonsäuren dieser Verbindungen verwendet werden. Der Begriff der Partialester schließt erfindungsgemäß sowohl den Fall ein, dass ein Teil der sauren Hydroxylgruppen der ionogenen Gruppe teilweise verestert ist, als auch den Fall, worin in den Polymerteilchen ein Teil der Hydroxylgruppen verestert ist, ein anderer Teil nicht verestert ist.Phosphoric acid esters of hydroxy-functional polymerizable C =C double bond-containing monomers preferably have the following formulas (I) or (II) of the following methacrylate compounds:

wherein R is a divalent organic group, such as in particular C1 to C10 alkylene. Preferably, R is a C 2 -C 4 alkylene group (ie, a C 2 -C 4 alkanediyl group), such as methylene, ethylene or n-propylene. Salts of these compounds are also applicable, such as, in particular, alkali metal salts, preferably the sodium salt or ammonium salts. The corresponding acrylates can also be used. Furthermore, partial esters can be used with other saturated or unsaturated carboxylic acids of these compounds. The concept of Partia According to the invention, ester includes both the case that a part of the acidic hydroxyl groups of the ionic group is partially esterified, and the case in which one part of the hydroxyl groups is esterified in the polymer particles, another part is not esterified.

Of the Proportion of polymerized ionogenic groups having functional Monomers are preferably from 0.1 to 100% by weight, more preferably 0.2 to 99.5 wt .-% based on the total amount of the monomers. This means that even homopolymer of these carrying ionic groups Monomers can be used. For example, you can at least 10% by weight, at least 20% by weight or at least 30% by weight of these monomers are present.

The ionogenic groups -OSO ₃ H and -OP (O) (OH) ₂ can also be obtained, for example, by reaction of hydroxyl-modified polymer particles (as obtained by copolymerization of hydroxyalkyl (meth) acrylates) or by addition of sulfuric or phosphoric acid to epoxide-containing (for example Glycidylmethacrylathaltige) polymer particles with sulfuric acid or phosphoric acid, by addition of sulfuric acid or phosphoric acid to double bond-containing polymer particles, by decomposition of persulfates or perphosphates in the presence of double bond-containing polymer particles, as well as by transesterification after the polymerization in the polymer particles are introduced, Furthermore, the groups -SO ₃ H and -P (O) (OH) _{2 can} also be introduced by sulfonation or phosphonation of vinyl aromatic polymers.

ionogenic Groups can also be modified by reaction of hydroxyl Polymer particles made with appropriately functionalized epoxides become.

Next The mentioned ionogenic groups can be further functional Groups for controlling the properties, especially in the surface the polymer particles are introduced, as by chemical reaction the already crosslinked polymer particles with respect to C = C double bonds reactive chemicals. These reactive chemicals are in particular such compounds, with the help of polar groups such. For example aldehyde, Hydroxyl, carboxyl, nitrile, etc. as well as sulfur-containing groups, such as Mercapto, dithiocarbamate, polysulfide, xanthogenate and / or dithiophosphoric acid groups and / or unsaturated Dicarboxylic acid groups chemically bonded to the polymer particles can be. The aim of the modification is in particular the Improvement of the compatibility with a matrix polymer, in which the polymer particles are optionally incorporated, for example, a good distributability in the production as well to achieve a good coupling.

Especially preferred methods of modification are the grafting of the polymer particles with functional monomers and the reaction with low molecular weight Agents. In this way, if necessary, the ionogenic, proton donating or proton accepting monomers be introduced into the polymer particles.

For the grafting of the polymer particles with functional monomers goes it is expedient from the aqueous Micro-gel dispersion which can be made with polar monomers such as vinylsulfonic acid, Styrenesulfonic acid, acrylic acid, methacrylic acid, Itaconic acid, hydroxyethyl (meth) acrylate (The term "(meth) acrylate" includes both methacrylate and acrylate in the present application), Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, acrylonitrile, Acrylamide, methacrylamide, acrolein, phosphonic acid or Phosphoric acid group-containing monomers with polymerizable C = C double bonds, such as vinylphosphonic acid, 2-phosphonomethylacrylic acid and 2-phosphonomethylacrylamide, phosphonic acid or phosphoric acid ester of hydroxy-functional, polymerizable C = C double bond-containing monomers or salts or derivatives, Partialester in particular under the conditions of a realizes radical emulsion polymerization. That way Obtained polymer particles with a core / shell morphology. It is desirable that in the modification step used monomer as quantitatively as possible on the unmodified Grafted polymer or microgel grafted. Conveniently, be the functional monomers before the complete Crosslinking of the microgels added.

Also a modification of double bond-containing polymer particles, such as. B. by ozonolysis comes into question.

In a preferred embodiment, the polymer particles, in particular the microgels, are modified by hydroxyl groups, in particular also on the surface thereof. The hydroxyl group content of the polymer particles, in particular of the microgels, is determined by reaction with acetic anhydride and titration of the acetic acid released in this case with KOH according to DIN 53240 as hydroxyl number with the dimension mg KOH / g polymer certainly. The hydroxyl number of the polymer particles, especially the microgels, is preferably between 0.1-100, more preferably between 0.5-50 mg KOH / g polymer.

The The amount of modifier used depends on its Effectiveness and individual requirements in the range of 0.05 to 30 weight percent, based on the total amount on polymer particles used, in particular microgel, especially preferred are 0.5-10 weight percent based on total amount on polymer particles, in particular microgel.

The Modification reactions can take place at temperatures of 0-180 ° C, preferably 20-95 ° C, optionally under pressure of 1-30 bar. The modifications can on rubber microgels in bulk or in the form of their dispersion in the latter case inert organic solvents or also water can be used as a reaction medium. Particularly preferred is the modification in aqueous Dispersion of the crosslinked rubber performed.

• – als Katalysator in säurekatalysierten Reaktionen, wie die Oligomerisierung von Isobuten, die säurekatalysierte Herstellung von Bisphenol A, Veresterungsreaktionen, Friedel-Crafts-Acylierungen und -Alkylierungen oder Dehydratisierungsreaktionen,
• – als stationäre Phase in Säulen und Platten für Trennoperationen,
• – insbesondere aufgrund ihrer potentielle Protonenleitfähigkeit zum Einsatz in elektrochemischen Verfahren,
• – zum Einsatz in Ionenabsorptionsverfahren,
• – insbesondere aufgrund ihrer protonenspendenden Brönstedtsäuren als Antifouling-Wirkstoffe in Formkörpern oder Beschichtungen, Beschichtungsmitteln, Anstrichmitteln, in Funktionsbekleidung bzw. in darin enthaltenen Fasern,
• – als antimikrobielle Bestandteile in medizinischen Anwendungen,
• – allgemein eingebettet in Polymermatrices, wie in der Form von Formkörpern, wie Folien oder Membranen, wie für Brennstoffzellen (s. DE-A-102004009396 ),
• – in deprotonierter Form als Hydrolyseschutzmittel in Polymermatrices,

sämtlich in heterogenen Prozessen bzw. Verfahren an denen Phasengrenzen, insbesondere fest/flüssig, fest/gasförmig beteiligt sind.The polymer particles whose preparation can be carried out as described above are suitable, for example

• As a catalyst in acid-catalyzed reactions, such as the oligomerization of isobutene, the acid-catalyzed preparation of bisphenol A, esterification reactions, Friedel-Crafts acylations and alkylations or dehydration reactions,
• As a stationary phase in columns and plates for separation operations,
• In particular due to its potential proton conductivity for use in electrochemical processes,
• For use in ion absorption processes,
• In particular because of their proton donating Bronsted acids as antifouling agents in moldings or coatings, coating compositions, paints, in functional clothing or in fibers contained therein,
• - as antimicrobial ingredients in medical applications,
• Generally embedded in polymer matrices, such as in the form of shaped articles, such as films or membranes, as for fuel cells (see FIG. DE-A-102004009396 )
• In deprotonated form as a hydrolysis protection agent in polymer matrices,

all involved in heterogeneous processes or processes in which phase boundaries, in particular solid / liquid, solid / gaseous.

In the polymer matrices, such as in the form of moldings, membranes, Films etc. can be used according to the invention Polymer particles in a proportion of matrix polymer to polymer particles from 1:99 to 99: 1, preferably from 10:90 to 90:10, more preferably Be contained 20:80 to 80:20. The amount of the invention used Polymer particles depend on the desired properties the shaped body, such as proton conductivity of the membranes.

Suitable matrix polymers are, for example, thermoplastic polymers such as standard thermoplastics, so-called techno-thermoplastics and so-called high-performance thermoplastics (cf. HG Elias Macromolecules Volume 2, 5 ed., Hüthig & Wepf Verlag, 1992, page 443 ff ), such as polypropylene, polyethylene, such as HDPE, LDPE, LLDPE, polystyrene, etc. and polar thermoplastic materials, such as PU, PC, EVM, PVA, PVAC, polyvinyl butyral, PET, PBT, POM, PMMA, PVC, ABS, AES, SAN, PTFE, CTFE, PVF, PVDF, polyimides, PA, in particular PA-6 (nylon), more preferably PA-4, PA-66 (Perlon), PA-69, PA-610, PA-11, PA -12, PA 612, PA-MXD6, etc. The weight ratio of these matrix polymers to the polymer particles may suitably be from 1:99 to 99: 1, preferably from 10:90 to 90:10, particularly preferably from 20:80 to 80:20. Preferred matrix polymer for use in polyelectrolyte membranes, in particular for fuel cells, is polybenzimidazole (eg. US 4460763 ).

The invention further relates to novel polymer particles having a mean particle diameter in the range of 5 to 500 nm (determined by ultracentrifugation as set forth above) obtained by emulsion polymerization containing ionogenic groups selected from the group consisting of: -SO ₃ H, -OSO ₃ H, -P (O) (OH) ₂ , -OP (OH) ₂ and -OP (O) (OH) ₂ and / or their salts and / or derivatives thereof. -SO ₃ H, -OSO ₃ H, -P (O) (OH) ₂ , -OP (O) (OH) ₂ and / or their salts and / or derivatives thereof are preferred, in particular esters, such as partial esters.

Of the Proportion of said ionogenic groups in the polymer is preferably in the range of 0.1 to 95% by weight, more preferably 1 to 90 Wt .-% based on the total amount of the polymer particles.

suitable Salts of the polymer particles include metal or ammonium salts, in particular alkali metal salts, alkaline earth metal salts, etc.

suitable Derivatives of the polymer particles include, in particular, and partial esters of said ionogenic groups.

The Invention is with regard to the applications of these new polymer particles not limited, and they can be in all applications already described above are used. The In particular, however, the invention relates to new composite materials of the above polymer particles, wherein these at least a carrier material are applied or incorporated therein. Such support materials include inorganic and organic materials, for example: carbon black, silica, Calcium carbonate, calcium oxide, magnesium oxide, aluminum oxide, barium sulfate, Zeolites, ion exchange resins, fibers, in particular polymer fibers Etc.

The but new polymer particles can also in pure form, for example used in ion exchange or catalytic processes become.

The Invention further relates to novel moldings, in particular Films in which the above-mentioned polymer particles in particular contained in a polymer matrix. In the polymer matrices, as in the shape of moldings, membranes, films, etc. can the polymer particles used in the invention in a proportion of matrix polymer to polymer particles 1:99 to 99: 1, preferably from 10:90 to 90:10, more preferably from 20:80 to 80:20 be included. To achieve certain properties of the shaped body, such as Proton conductivity can be a certain proportion, such as also exceeded at least 30 wt .-% or at least 40 wt .-% be as long as the mechanical properties of the molding allow this. With regard to the preferred matrix polymers to the above statements.

EXAMPLES:

Production examples for the microgels

following the preparation of the microgels is described in the other Examples are used.

All Microgels were prepared by emulsion polymerization. The monomer combinations used for the preparation of the microgels as well as essential formulation ingredients are given in Tables 1) and 2). All recipe ingredients will be based on 100 parts by weight of the monomer mixture.

In Table 1), the experiments are summarized in which 95 Lanxess Germany GmbH was used as an emulsifier Mersolat® ^® H. Mersolat H 95 ^® is the sodium salt of a mixture of long-chain (C16-C18) alkyl sulfonates.

In Table 2) the experiments are summarized in which as an emulsifier a mixture of disproportionated rosin acid (Dresinate ^® 731/70% strength (of Abieta) and fatty acid Edenor ^® HTICI N from Oleo Chemicals / 12% strength in water was used). In addition, 0.6 part by weight of potassium hydroxide was added to these experiments (Table 2). Due to the amount of potassium hydroxide, the mixture of resin and fatty acid was formally neutralized to 150%.

• Styrol (98%ig) von KMF Labor Chemie Handels GmbH
• Butadien (99%ig, entstabilisiert) der Lanxess Deutschland GmbH
• Trimethylolpropantrimethacrylat (90%ig) von Aldrich; Produktnummer: 24684-0 (Abkürzung: TMPTMA)
• Hydroxyethylmethacrylat (96%) von Acros; Produktnummer: 156330010 (Abkürzung: HEMA)
• Na-Vinylsulfonat; 30%ige wässrige Lösung von Fluka; Produktnummer: 95061 (Abkürzung: NaVS)
• Na-Styrolsulfonat (90%) von Fluka; Produktnummer: 94904 (Abkürzung: NaSS)
• Vinylphosphonsäure (95%) von Fluka, Produktnummer: 95014 (Abkürzung: H₂VP)
• 2-(Methacryloyloxy)ethyl Phosphat von Aldrich, Produktnummer: 463337 (Abkürzung: H₂MOOEP)

The following monomers were used for the preparation of the microgels listed in Tables 1) and 2):

• Styrene (98%) from KMF Laboratory Chemistry GmbH
• Butadiene (99%, destabilized) of Lanxess Germany GmbH
• Trimethylolpropane trimethacrylate (90%) from Aldrich; Product number: 24684-0 (Abbreviation: TMPTMA)
• Hydroxyethyl methacrylate (96%) of Acros; Product number: 156330010 (abbreviation: HEMA)
• Sodium vinyl sulfonate; 30% aqueous solution of Fluka; Product number: 95061 (Abbreviation: NaVS)
• Na styrenesulfonate (90%) from Fluka; Product number: 94904 (Abbreviation: NaSS)
• Vinylphosphonic acid (95%) from Fluka, product number: 95014 (abbreviation: H ₂ VP)
• 2- (Methacryloyloxy) ethyl phosphate from Aldrich, product number: 463337 (abbreviation: H ₂ MOOEP)

The Products OBR 1290-2, OBR 1290-4, OBR 1293-1, OBR 1291-1, OBR 1297, OBR 1294-1 and OBR 1438-1 (Table 1) were placed in a 61 glass reactor made with stirrer while the products OBR 1361-B, OBR 1435-4, OBR 1327 B and OBR 1330 I (Table 1 and Figs Table 2) Prepared in a 20 l steel autoclave with stirrer were.

When carrying out the emulsion polymerizations in the glass reactor, 3.93 kg of water were introduced in each case and rinsed with a stream of nitrogen. A portion of the total amount of mersolate was added to the water blanket and dissolved. In experimental OBR 1290-2, 5.3 g of Mersolat H 95 ^®; at OBR 1291-1 13.7 g of Mersolat H 95 ^®; at OBR 1293-1, OBR 1297 OBR 1294-1, 1361-B and OBR OBR 1438-1 24.2 g of Mersolat H 95 ^® as well as OBR 1290-4 40.0 g Mersolat H ^® 95 were in the water were given and solved. Thereafter, 1000 g of the monomer mixtures listed in Table 1) were added to the reaction vessel along with 0.08 g of 4-methoxyphenol (Arcos Organics, Item No. 126001000, 99%). After heating the reaction mixture to 30-40 ° C, a freshly prepared 4% aqueous premix solution was added. This premix solution consisted of:
0.169 g of ethylenediaminetetraacetic acid (Fluka, article number 03620),
0.135 g of iron (II) sulfate · 7H ₂ O (Riedel de Haen, article number 12354), (calculated without water of crystallization)
0.347 g of Rongalit C, Na formaldehyde sulfoxylate 2-hydrate (Merck-Schuchardt, article number 8.06455) (calculated without water of crystallization) and
0.524 g of trisodium phosphate · 12H ₂ O (Acros, article number 206520010) (calculated without water of crystallization) are metered in.

For activation of the polymerization became an activator solution from 0.56 g of p-menthane hydroperoxide (Trigonox NT 50 from Akzo-Degussa) in 50 g of water and the residual amount of Mersolat K30 / 95 (2.1 g).

The Half of the aqueous activator solution was added 5 min. after addition of the premix solution in the Reaction vessel given. This became the polymerization After 2.5 hours of reaction time, the reaction temperature became increased to 40-50 ° C. After another Hour became the second half of the aqueous activator solution added. Upon reaching a polymerization conversion> 90% (usually: 95% -100%) was the polymerization by addition of an aqueous Solution of 2.35 g of diethylhydroxylamine (DEHA, Aldrich, article number 03620) stopped.

The Experiments OBR 1361-B, OBR 1327 B and OBR 1 330 I were in analog Manner in a 20 liter autoclave with stirrer performed. The autoclave batches were each 3.5 kg of the monomer mixture and a total water volume of 14 kg used, the further implementation The experiments were carried out in an analogous manner as in the glass reactor described experiments.

To the stopping of the polymerization reactions were unreacted Monomers and volatiles by stripping with Steam removed from the latex.

The latexes of Table 1) and 2) were filtered and as in Example 2 of US 6399706 mixed with stabilizer, coagulated and dried.

The Gels were both in the latex state by ultracentrifugation (UZ) and by dynamic light scattering (DLS) in terms of particle diameter and as a solid in terms of solubility in toluene (gel content, swelling index / QI) and by means of DSC (glass transition temperature / Tg and width of the Tg step).

characteristic Data for the microgels described in Tables 1) and 2) in Table 3).

d₁₀, d₅₀ und d₈₀:

Die Teilchendurchmesser wurden am abgestoppten und mit Wasserdampf gestrippten Latex mittels Ultrazentrifugation bestimmt (W. Scholtan, H. Lange, „Bestimmung der Teilchengrößenverteilung von Latices mit der Ultrazentrifuge", Kolloid-Zeitschrift und Zeitschrift für Polymere (1972) Band 250, Heft, 8). Die Latices haben eine charakteristische Teilchengrößenverteilung die durch die Durchmesserangaben d₁₀, d₅₀ und d₈₀ beschrieben wird. Diese Durchmesserangaben bedeuten, dass jeweils 10 Gew.% (d₁₀), 50 Gew.-% (d₅₀) und 80 Gew.-% (d₈₀) der Teilchen einen Durchmesser besitzen, der kleiner als der angegebene Zahlenwert ist. Die Teilchengröße der Mikrogele im Latex und in den aus dem Latex isolierten Festprodukten wie sie in den erfindungsgemäßen Zusammensetzungen eingesetzt werden, sind praktisch identisch.

d_dls:

am Latex bestimmter Teilchendurchmesser, der mittels dynamischer Lichtstreuung (DLS) erhalten wurde. Für die Bestimmung wurde ein Zetasizer^® Nano Instrument (Modellnummer: Nano ZS) von Malvern Instruments Ltd., Worcestershire, England verwendet. Mittels dynamischer Lichtstreuung wird ein mittlerer Teilchendurchmesser erhalten.

Tg:

Glastemperatur

ΔTg:

Breite der Tg-Stufe Für die Bestimmung von Tg und ΔTg wurde das Gerät DSC-2 von Perkin-Elmer benutzt. Im ersten Messzyklus wird die Probe mit flüssigem Stickstoff mit 320 K/min. auf –130°C abgekühlt und mit einer Heizrate von 20 K/min. auf 150°C aufgeheizt. Im zweiten Messzyklus wird wiederum auf –130°C gekühlt und mit 20 K/min. aufgeheizt. Tg und ΔTg werden im 2. Messzyklus bestimmt.

In Table 3) mean:

d ₁₀ , d ₅₀ and d ₈₀ :

The particle diameters were determined on stopped and steam-stripped latex by ultracentrifugation (W. Scholtan, H. Lange, "Determination of the Particle Size Distribution of Latexes with the Ultracentrifuge", Kolloid-Zeitschrift and Zeitschrift fur Polymere (1972) Vol 250, Heft, 8) The latices have a characteristic particle size distribution which is described by the diameter data d ₁₀ , d ₅₀ and d _80. These diameter data mean that in each case 10% by weight (d ₁₀ ), 50% by weight (d ₅₀ ) and 80% by weight. -% (d ₈₀₎ of particles have a diameter which is smaller than the specified numerical value the particle size of the microgels in the latex and in the isolated from the latex solid products such as are used in the compositions of this invention are virtually identical..

d _dls :

Particle diameter determined on latex, which was obtained by means of dynamic light scattering (DLS). (Model Number: Nano ZS) for determining a Zetasizer ^® Nano Instrument was developed by Malvern Instruments Ltd., Worcestershire, England used. By means of dynamic light scattering, an average particle diameter is obtained.

Tg:

glass transition temperature

.DELTA.Tg:

Width of the Tg step The DSC-2 device from Perkin-Elmer was used to determine Tg and ΔTg. In the first measurement cycle, the sample is mixed with liquid nitrogen at 320 K / min. cooled to -130 ° C and at a heating rate of 20 K / min. heated to 150 ° C. In the second measuring cycle, it is again cooled to -130 ° C and at 20 K / min. heated. Tg and ΔTg are determined in the 2nd measuring cycle.

to Determination of insoluble content (gel content) and of Swelling index (QI) was 250 mg of the microgel in 25 ml of toluene Swollen with shaking at 23 ° C for 24 hours. After centrifugation at 20,000 rpm, the insoluble Part separated and dried.

Of the Gel content results from the quotient of the dried residue and the weight and is given in weight percent.

The swelling index QI is calculated from the weight of the solvent-containing microgel swollen in toluene at 23 ° C for 24 hours (after centrifugation at 20,000 rpm) and the weight of the dry microgel according to the following formula: QI = wet weight of the microgel / dry weight of the microgel.

Examples of use for the polymer particles, prepared by emulsion polymerization

Copper adsorption of vinylphosphonate and vinylsulfonate containing gels of 0.32 molar aqueous Copper sulfate solution

10 g of gels OBR 1297 and OBR 1361 B were dissolved in 75 ml of a 0.32 molar aqueous solution of copper sulfate (CuSO ₄ .5H ₂ O from Aldrich, article number 20,920-1) to demonstrate the affinity of vinylphosphonate and vinylsulfonate gels for copper. dispersed with stirring for 24 h. Thereafter, the gels were filtered off and dried to constant weight at 60 ° C. The metal contents of the gels indicated in the above table were measured before and after treatment with copper solution by inductively coupled radio frequency plasma atomic emission spectroscopy (AES-ICP). [Http://www.schulchemie.de/atomems1.htm] certainly. Ca content [ppm] Na content [ppm] Cu content [ppm] OBR 1297 (original sample) 2900 6900 11 OBR 1297 (after treatment with Cu sulphate solution) 620 350 15000 OBR 1361 B (original sample) 5.2 360 <1 OBR 1361 B (after treatment with Cu sulphate solution) 1.4 120 3200

As shown in the above experiments, alkali and alkaline earth metals are used in copper adsorption displaced by the copper. Both the vinylphosphonate-containing gel (OBR 1297) and the vinylsulfone-containing gel (OBR 1361 B) have a high capacity for the adsorption of copper ions.

Copper adsorption from 0.01 molar Cu sulphate solution

To demonstrate copper adsorption from dilute aqueous solutions, 20 g of the vinylphosphonated gel OBR 1297 were dispersed in 225 ml of a 0.01 molar aqueous solution of copper sulfate (CuSO ₄ .5H ₂ O from Aldrich, article number 20,920-1). After 24 hours, the gel was separated and dried at 60 ° C. Using AES-ICP, the Cu content of the gel was determined to be 7200 ppm. This experiment demonstrates that the OBR 1297 vinylphosphonate gel is suitable for near quantitative removal of copper from dilute effluents.

Silver adsorption from 0.1 molar silver nitrate solution

to Demonstration of the ability to adsorb silver 10 g of the vinylphosphonate-containing gel OBR 1297 in 75 ml of a 0.1 molar aqueous solution of silver nitrate (Merck, Article number: 1512) with stirring for 24 h. After that The gel was filtered off and to constant weight at 60 ° C. dried. AES-ICP silver levels were before and after the treatment with silver nitrate solution. It was found that the unexposed original gel contained <1 ppm silver. After treatment with silver nitrate solution, the silver content was 78,000 ppm. As a result, with the help of the gel about 96% of the available standing amount of silver from the aqueous solution were adsorbed. The experiment shows that the vinylphosphonate-containing Gel for the removal of silver from wastewater suitable is.

Zinc adsorption from 0.0094 molar zinc sulfate solution

to Demonstration of zinc adsorption from a dilute solution were 20 g of the gel OBR 1297 in 200 ml of a 0.0094 molar aqueous Solution of zinc sulphate (Fluka, article number: 96500) (contains 614.5 mg zinc in total) with stirring for 24 h. Thereafter, the gel was filtered off and added to constant weight Dried 60 ° C. The zinc content of the gel was before (<1 ppm) and after Treatment (6900 ppm) with zinc solution determined by AES-ICP. With o. G. An example is the high affinity of the phosphonate-modified gels demonstrated for zinc ions.

Copper adsorption of hydroxyl-containing Gels after activation with sulfuric acid or phosphoric acid

The two hydroxyl-containing gels OBR 1327 B and OBR 1330 I were first treated with sulfuric acid (50 g gel in 250 ml sulfuric acid / 10%) or with phosphoric acid (50 g gel in 250 ml phosphoric acid / 10% 24 h at 96 ° C. , isolated by filtration, redispersed in water and washed to neutrality with deionized water and dried at 60 ° C. Thereafter, in each case 10 g of the acid-treated gel in a 0.32 molar aqueous solution of copper sulfate (CuSO ₄ .5H ₂ O from Aldrich, article number 20,920-1) with stirring for 24 h.

Thereafter, the gels were filtered off and dried to constant weight at 60 ° C. The contents of selected metals were determined both before (original samples) and after treatment with acid / copper solution using AES-ICP (see following table). Ca content [ppm] Na content [ppm] Cu content [ppm] OBR 1327 B (original sample) 2400 37 <1 OBR 1327 B / after treatment with: 1) H ₂ SO ₄ 2) Cu sulphate solution 1900 16 590 OBR 1327 B / after treatment with: 1) H ₃ PO ₄ 2) Cu sulphate solution 2000 22 750 OBR 1330 I (original sample) 1400 45 1.2 OBR 1330 I / after treatment with: 1) H ₂ SO ₄ 2) Cu sulphate solution 1200 31 1300 OBR 1330 I / Treatment with: 1) H ₃ PO ₄ 2) Cu sulphate solution 1300 30 1700

With The experiments show that hydroxyl-containing gels both after activation with sulfuric acid as well as after activation with phosphoric acid for the adsorption of copper capable are.

Condensation of 2-ethylhexanol with benzoic acid based on gels containing acid groups

Schema 1: Kondensation von 2-Ethylhexanol mit Benzoesäure To demonstrate the suitability of the polymer particles as regenerable catalysts for acidic esterifications, the following experiments are carried out with vinylphosphonate- and vinylsulfonate-containing gels. The condensation takes place in substance at 150 ° C. There is no solvent used. The benzoic acid and 2-ethylhexanol have been commercially obtained from Aldrich. The amount of catalyst is 0.02 acid equivalents. It is assumed that the acid groups from the microgel synthesis are completely accessible. The progress of the reaction is followed by means of gas chromatography. In all the approaches described below, the molar ratio of benzoic acid to 2-ethylhexanol is one to three, so that it is possible to dispense with a repeated statement. The test reaction is the condensation of 2-ethylhexanol with benzoic acid as shown in Scheme 1.

Scheme 1: Condensation of 2-ethylhexanol with benzoic acid

1. Esterification with microgel OBR 1361-B as a catalyst

The experiment is carried out in an apparatus with a water separator and passing over nitrogen. Approach: 6,40g Microgel OBR 1361 B (with H ₂ SO ₄ , 10% activated) 97,00g 2-ethylhexanol (anhydrous) 3 eq 30,32g benzoic acid 1 eq

Execution:

6.40 g microgel OBR 1361 B before the start of the experiment at room temperature for 4 days in 97.0 g of anhydrous 2-ethylhexanol swollen with repeated stirring. The benzoic acid is added portionwise at room temperature. By passing nitrogen is heated to 150 ° C within 50 minutes and stirred for 6 hours at 150 ° C and passing nitrogen. An hourly small sample is taken for GC measurement. These samples are blank. After the end of the reaction, the microgel is filtered off, extracted and dried in a vacuum oven at 80 ° C and 100 mbar to constant weight. The microgel is returned virtually quantitatively. The development of sales is documented in Table 1. Table 1: Reaction with the aid of microgel OBR 1361 B Time [min] Amount of alcohol [%] Amount of acid [%] Amount of ester [%] 60 71 11 18 120 65.5 8th 26.5 180 62 6 32 240 59 5 36 300 57 3.5 39.5 360 55.5 3 41.5

The Percentages are area percentages in the GC.

2. Esterification with microgel OBR 1297 as catalyst

The experiment is carried out in an apparatus with a water separator and passing nitrogen over. approach 7.38 g Microgel OBR 1297 (with H ₂ SO ₄ , 10% activated) 97.00 g 2-ethylhexanol (anhydrous) 3 eq 30.32 g benzoic acid 1 eq

Execution:

7.38 g of microgel OBR 1297 is swollen for 4 days in 97.0 g of anhydrous 2-ethylhexanol with repeated stirring at room temperature for 4 days before the start of the experiment. While passing over nitrogen, the mixture is heated to 150 ° C. in the course of 50 minutes and stirred at 150 ° C. for 6 hours and nitrogen is passed over. An hourly small sample is taken for GC measurement. These samples are blank. After the end of the reaction, the microgel is filtered off, extracted and dried in a vacuum oven at 80 ° C and 100 mbar to constant weight. The microgel is returned virtually quantitatively. The evolution of sales is documented in Table 2. Table 2: Reaction with the aid of microgel OBR 1297: Time [min] Amount of alcohol [%] Amount of acid [%] Amount of ester [%] 60 78 15 7 120 75 14 11 180 72.5 13 14.5 240 70.5 12 17.5 300 68.5 10.5 21 360 67.5 9.5 23

The Percentages are area percentages in the GC.

3. Esterification without microgel as a comparative experiment

The experiment is carried out in an apparatus with a water separator and passing nitrogen over. approach 97.00 g 2-ethylhexanol (anhydrous) 3 eq 30.32 g benzoic acid 1 eq

Execution:

The 2-ethylhexanol is initially charged and stirred vigorously the benzoic acid added in portions at room temperature. It arises after a short stirring a blank solution.

While passing over nitrogen, the mixture is heated to 150 ° C. in the course of 50 minutes and stirred at 150 ° C. for 6 hours and nitrogen is passed over. An hourly small sample is taken for GC measurement. These samples are blank. Table 3: Reaction without the aid of microgel as comparative experiment: Time [min] Amount of alcohol [%] Amount of acid [%] Amount of ester [%] 60 80.2 16.2 3.6 120 78.4 15.3 6.3 180 76.7 14.5 8.8 240 75.4 13.3 11.3 300 73.8 12.7 13.6 360 72.7 11.9 15.4

The Percentages are area percentages in the GC.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 2005/033185 [0004]
• US 2187146 [0026]
• US 5302696 [0034]
• US 5442009 [0034]
• - DE 102004009396 A [0056]
• US 4460763 [0058]
• - US 6399706 [0077]

Cited non-patent literature

• - Römpp Lexikon der Chemie, Volume 2, 10th edition 1997; PA Lovell, MS EI-Aasser, Emulsion Polymerization and Emulsion Polymers, John Wiley & Sons, ISBN: 0 471 96746 7; H. Gerrens, Fortschr. Hochpolym. Forsch. 1, 234 (1959) [0008]
• - HG Müller (1996) Colloid Polymer Science 267: 1113-1116 and W. Scholtan, H. Lange (1972) Kolloid-Z u. Z. Polymers 250: 782 [0019]
• - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/2, page 848 [0033]
• - HG Elias Macromolecules Volume 2, 5 ed., Hüthig & Wepf Verlag, 1992, page 443 et seq. [0058]
• - [http://www.schulchemie.de/atomems1.htm] [0084]

Claims (27)

Use of by emulsion polymerization produced polymer particles having an average particle diameter in the range of 5 to 500 nm, containing ionogenic groups, as proton donating and / or proton-accepting substance in heterogeneous chemical Processes. Use according to one of the preceding claims, wherein the polymer particles surface and / or contain non-surface-active ionogenic groups, Use according to one of the preceding claims, wherein the polymer particles produced by emulsion polymerization are rubbery or non-rubbery. Use according to one of the preceding claims, wherein the rubbery polymer particles are those based on conjugated dienes such as butadiene, isoprene, 2-chlorobutadiene and 2,3-dichlorobutadiene, and ethene, esters of acrylic and methacrylic acid, vinyl acetate, Styrene or derivatives thereof, acrylonitrile, acrylamides, methacrylamides, Tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, double bond-containing Hydroxy compounds such. B. hydroxyethyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acrylate, hydroxybutyl methacrylate, acrolein or combinations thereof. Use according to one of the preceding claims, wherein the polymer particles have a glass transition temperature, Tg, from -100 ° C to 150 ° C have. Use according to one of the preceding claims, wherein the polymer particles are based on methacrylates, in particular Methyl methacrylate, styrene or styrene derivatives, such as alpha-methylstyrene, para-methylstyrene, acrylonitrile, methacrylonitrile, vinylcarbazole or Combinations of these are. Use according to one of the preceding claims, wherein the polymer particles produced by emulsion polymerization at least partially cross-linked. Use according to one of the preceding claims, wherein the polymer particles produced by emulsion polymerization at least partially by the addition of polyfunctional monomers are crosslinked in the polymerization, Use according to claim 8, wherein the polyfunctional Monomers are selected from the group consisting from: compounds having at least two, preferably 2 to 4 copolymerizable C = C double bonds, such as diisopropenylbenzene, divinylbenzene, divinyl ether, Divinyl sulfone, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, N, N'-m-phenylenemaleimide, 2,4-tolylenebis (maleimide), Triallyl trimellitate, acrylates and methacrylates of polyvalent, preferably 2- to 4-valent C 2 to C 10 alcohols, such as ethylene glycol, Propandiol-1,2, butanediol, hexanediol, polyethylene glycol with 2 to 20, preferably 2 to 8 oxyethylene units, neopentyl glycol, bisphenol A, Glycerol, trimethylolpropane, pentaerythritol, sorbitol and unsaturated Polyesters of aliphatic di- and polyols and maleic acid, Fumaric acid, and / or itaconic acid. Use according to one of the preceding claims, wherein the polymer particles are approximately spherical Have geometry. Use according to one of the preceding claims, wherein the polymer particles have an average particle diameter of less than 350 nm. Use according to one of the preceding claims, wherein the polymer particles are insoluble in toluene at 23 ° C Have levels of at least about 70 wt .-%. Use according to one of the preceding claims, wherein the polymer particles in toluene at 23 ° C a swelling index less than about 80. Use according to one of the preceding claims, wherein the polymer particles have a width of the glass transition region greater than about 5 ° C. Use according to any one of the preceding claims, wherein the ionogenic groups are selected from one or more of the following functional groups: -COOH, -SO ₃ H, -OSO ₃ H, -P (O) (OH) ₂ , -OP (OH) ₂ and -OP (O) (OH) ₂ and / or their salts and / or their derivatives. Use according to one of the preceding claims, wherein the ionogenic groups by copolymerization accordingly functionalized monomers and / or by modification according to the Polymerization are introduced into the polymer particles. Use according to claim 16, wherein the functionalized Monomers are selected from the group consisting of: Acrylic acid, methacrylic acid, vinylbenzoic acid, Itaconic acid, maleic acid, crotonic acid, fumaric acid, Vinylsulfonic acid, styrenesulfonic acid, containing phosphonic acid groups Monomers with polymerizable C = C double bonds, such as vinylphosphonic acid, 2-phosphonomethylacrylic acid and 2-phosphonomethylacrylamide, Phosphoric acid or phosphonic acid esters of hydroxy-functional, polymerizable C = C double bond-containing monomers or Salts or derivatives thereof, Use according to claim 17, wherein the phosphoric acid esters of hydroxy-functional polymerizable C =C double bond-containing monomers have the following formulas (I) to (II):

wherein R is a divalent organic group, such as in particular C1 to C10 alkylene. Use according to any one of the preceding claims, wherein the ionic groups are -OSO ₃ H or -OP (O) (OH) ₂ obtained by reaction of hydroxyl-modified polymer particles with sulfuric acid or phosphoric acid, by addition of sulfuric acid or phosphoric acid to double-bond-containing polymer particles, by decomposition of persulfates or perphosphates in the presence of double-bond-containing polymer particles, as well as by transesterification by means of sulfuric or phosphoric acid are introduced into the polymer particles. Use according to any one of the preceding claims, wherein the ionic groups -SO _{3 are} H or -P (O) (OH) ₂ and are introduced by sulfonation or phosphonation of vinyl aromatic polymers, Use according to one of the above-mentioned Claims, wherein the polymer particles - when Catalyst in acid-catalyzed reactions, such as the oligomerization of isobutene, the acid-catalyzed production of bisphenol A, esterification reactions, Friedel-Crafts acylations and alkylations or dehydration reactions are used, - when stationary phase in columns and plates for Separation operations are used - in electrochemical Procedures are used In ion absorption processes be used - Used as an antifouling agent become, - used in paints, - in Functional clothing are used, - in medical Articles are used, In polymer matrices, as in the form of shaped articles, such as films or membranes, as used for fuel cells, embedded, - in deprotonated form used as hydrolysis protection embedded become. Polymer particles having an average particle diameter in the range of 5 to 500 nm, obtained by emulsion polymerization, containing ionogenic groups selected from the group consisting of: -SO ₃ H, -OSO ₃ H, -P (O) (OH) ₂ , - OP (OH) ₂ and -OP (O) (OH) ₂ and / or their salts and / or derivatives thereof. Polymer particles according to claim 22, wherein the ionic Groups surface and / or non-surface are ionogenic groups. Polymer particles according to claim 23, wherein the derivatives be selected from esters. Use of the polymer particles according to one of the claims 22 to 24, - As a catalyst in acid-catalyzed Reactions, such as the oligomerization of isobutene, the acid-catalyzed Preparation of bisphenol A, esterification reactions, Friedel-Crafts acylations and -alkylations or dehydration reactions are used, - when stationary phase in columns and plates for Separation operations are used - in electrochemical Procedures are used In ion absorption processes be used - Used as an antifouling agent become, - used in paints, - in Functional clothing are used, - in medical Articles are used, In polymer matrices, as in the form of shaped articles, such as films or membranes, as used for fuel cells, embedded, - in deprotonated form used as hydrolysis protection embedded become. Composite material containing polymer particles after one of claims 22 to 24 and at least one carrier material. Shaped body comprising polymer particles according to one of claims 22 to 24.