DE19921103A1 - Chlorinated adsorber polymer, used e.g. for purification of industrial effluents, obtained by radical suspension polymerisation of divinylbenzene and ethylvinyl-benzene in presence of chloro-organic compounds - Google Patents

Abstract

Bead-shaped, chlorine-containing, highly porous adsorber polymers are produced by simultaneous dispersion or suspension polymerisation and chloromethylation of a mixture of 2-80 wt.% divinylbenzene (DVB) with ethylvinylbenzene and other monomers in presence of radical initiator(s) and 0.5-100 volume% (based on monomers) chloro-organic compounds. An Independent claim is also included for polymers obtained by this process.

Description

Field of application of the invention

In recent drives, organic pollutants such as e.g. B. phenols, chlorinated hydrocarbons or nitro compounds from industrial wastewater increasingly synthetic, pearl-shaped adsorber polymers based on styrene-divinylbenzene copolymers. These sorbents are highly porous materials with a large specific surface area, which have a number of advantages over good water purifying carbons:

• - greater adsorption capacity, mainly in the area of high pollutant concentrations,
• - better regenerability (less energy consumption than with activated carbon),
• - better mechanical and chemical stability,
• - Effective and energy-efficient recycling of the adsorbed substances.

If the adsorption capacity of the adsorber polymers used is exhausted, the Adsorber polymers can be regenerated by known methods. For example, the adsorbed substances are removed thermally. Even removal with the help of other gases, like water vapor is possible. Appropriate methods are known. (Acta hydrochim. hydrobiol. 19 (1991), 675-682, Chem. Techn. 42, August (1990), 335-338).

The adsorber polymers can be used as adsorbents for adsorption from a variety of Liquid phases are used. The expression "liquid phase" can be homogeneous Solutions, emulsions, dispersions, liquids containing gases in solution, and the like Include mixtures. A liquid serves as a carrier phase, from which substances from the Adsorber polymers are adsorbed.

The adsorbed compounds can after separation of the adsorbent from the Liquid by suitable methods, for example by heating, washing or Eluting to be released. The adsorber polymers show the adsorption of organic Water ingredients highly selective adsorption properties. So they are very good at Purification of industrial waste water or laboratory waste water can be used.

Above all, these include:

• - Dyes from dyeing waste water
• - plant protection products
• - Pharmaceuticals (e.g. antibiotics, enzymes, proteins and steroids)
• - Removal and recovery of fatty acids and fatty acids
• - Proteins (food industry)
• - surfactants (laundries)
• - separation of biological and synthetic molecules (HPLC, Exclusion Chromatography (SEG) and Reverse Phase Chromatography (RPC)
• - Separation of methanol from hydrocarbon streams (ETHEROL process)
• - Adsorbent for liquid or gas chromatography
• - Separation of organic gas mixtures
• - Cleaning of hydrochloric acid solutions (waste acid) from organic substances
• - Separation and recovery of organic vapors from hydrogen chloride gas
• - Recovery of unsaturated hydrocarbons from pyrolysis gas
• - De-phenolization and product recovery (e.g. in the production of bisphenol-A, Parathion, etc.)
• - Residual removal of chlorinated hydrocarbons
• - Treatment of bleaching waste in paper mills
• - Decolorization of cane sugar solutions and the cleaning of Hydrogen peroxide solutions.

In addition to cleaning liquids, the adsorber polymers can also be used to isolate organic compounds from liquids or liquid mixtures are used. The goal here is the isolation and extraction of organic compounds, some of them highly diluted and among many other ingredients in liquids or Liquid mixtures are present. Here, the highly selective adsorption can Adsorber polymers are advantageously used to make organic compounds a variety of possibly similar organic compounds in a liquid isolate.

The organic compounds are preferably isolated from aqueous liquids. It is in particular also pharmaceutical active ingredients, which from the in their Manufacturing mother liquors are isolated.

Characteristic of the known technical solutions

In technology, adsorber polymers are made using a one- or two-stage process manufactured.

The one-step process delivers low to medium-high porous materials, the so-called latent porous adsorber polymers with specific surfaces of 300 to 600 m ² / g.

The two-stage process delivers the highly porous materials with specific surfaces from 800 to 1200 m ² / g.

Highly porous adsorber polymers are currently only used in a two-stage process Process manufactured. In the first stage, styrene is made with small amounts of Divinylbenzene (2-8%) without the addition of inert substances by suspension polymerization copolymerized. These intermediate products belong to the so-called real gel type, i.e. H. you are through Copolymerization of styrene with divinylbenzene without the aid of solvents or Precipitants or solvent-precipitant mixtures.

As a result of the first stage, insoluble, solid pearl-shaped styrene-divinylbenzene-Co is obtained polymers, depending on the degree of crosslinking (divinylbenzene content) in different organic Swell solvents to different extents.

In the second stage, the weakly cross-linked styrene-divinylbenzene copolymer is added suitable conditions. Post-networking is generally done with the help performed by monochlorodimethyl ether. The styrene-divinylbenzene copolymer Partially chloromethylated in a preceding step and simultaneously or in a separate step downstream step "with yourself", d. H. with other aromatic units of the polymer post-crosslinked (US-PS 4572905, US-PS 4675309, AT-PS 359980, DD-PS 249703, DD-PS 292850).

In the patent DE-PS 42 15 741 the already known process of chloromethylation and simultaneous or post-crosslinking with monochlorodimethyl ether Dispersion or suspension polymers consisting of styrene, ethylstyrene and divinylbenzene applied, however, these starting products to be used by radical Polymerization of the monomer mixtures in the presence of one or more organic Substances have been produced. Pre-products of the real gel type are not included Divinylbenzene contents between 0.1 and 8.0 wt .-% used, but mainly Styrene-ethylstyrene-divinylbenzene copolymers with divinylbenzene contents between 2 and 17 wt .-%, produced in the presence of selected inert, organic substances and / or halogenated, organic substances, whose carbon number between 1 and 6 and Halogen number is between 1 and 4. Typical representatives are e.g. B. dichloromethane, Dibromomethane, trichloromethane, tribromomethane, triiodomethane, carbon tetrachloride, Tetrabromomethane, chlorobromomethane, dichloroethane, dibromoethane, chlorobromomethane,  Trichloroethane, trichlorethylene, tetrachloroethane, tetrachlorethylene, dichloropropane, Dibromopropane, dichlorobutane, dibromobutane, chlorobromobutane, dichlorohexane, dibromohexane and others, as well as mixtures of the substances mentioned with other inert, organic Fabrics.

These polymers are used in the subsequent chloromethylation and simultaneous or postcrosslinked with monochlorodimethyl ether.

The patent does not describe the extent to which the chemical composition of the polymeric matrix due to the presence of one or more halogen-containing, organic Solvent changes during suspension polymerization. It also doesn't mention how high the specific surface area or the degree of swelling of the styrene-ethylstyrene-divinylbenzene-Co polymeric (content of divinylbenzene between 2 and 17 wt .-%).

Latent porous adsorber polymers are generally processed in a one-step process Suspension polymerization of styrene or other monomers with divinylbenzene as Crosslinking agent prepared in the presence of inert substances. Not reactive, organic Solvents are solvents that are in during radical suspension polymerization not be included in the polymerization process.

After the polymerization, the inert substances are removed from the polymer and are together with the amount of crosslinker responsible for the degree of porosity.

Depending on the procedure, medium to highly porous products are created with one pronounced adsorption power against polar and non-polar organic compounds. The inert substances are described in the patents as precipitants, solvents, porogen, Pore regulator, active ingredient, volatile agents, functional material, etc. described. They serve as solvents for the monomers and as precipitants for the resulting polymers.

The following can be used as inert agents: aliphatic and aromatic hydrocarbons, Alcohols, esters, ketones and soluble polymers. In this process, the porosity is and hence the size of the specific surface due to the type and composition of the Controllable inert substances (Ulbricht, J., Fundamentals of polymer synthesis, Akademieverlag Berlin 1978, 86-87, Elias, H.-G., Macromolecules, Hüthig and Wepf Verlag Basel Heidelberg 1975, 608-610.)

Already in 1957 the use of pore regulators such as e.g. B. isopropyl alcohol, ethanol, toluene, heptane and cyclohexane in the suspension polymerization. The adsorber polymers produced had specific surfaces of up to 500 m ² / g. The low surfaces are partly due to the water solubility of some pore regulators.

In the patent US-PS 3509078 polymeric materials such. B. polyethylene glycol and in the patent US-PS 3989649 paraffin wax used to represent the pores. The polymer Materials were then removed from the matrix by solvent extraction.

In the patent US-PS 3637535 gasoline was used as a pore regulator.

The patent DE-PS 30 00 596 also uses aromatic hydrocarbons described as a pore regulator, here only inert, non-reactive, organic Solvents such as E.g .: toluene, ethylbenzene, xylene, diethylbenzene, dodecylbenzene, hexane, Octane, dodecane, propyl alcohol, butyl alcohol, n-amyl alcohol, isoamyl alcohol, ethylene glycol, Use polyethylene glycol, propylene glycol, dipropylene glycol, nitromethane, nitroethane were. Here too, water-miscible alcohols were used as pore regulators.  

The use of a non-reactive, organic solvent is particularly in the Manufacture of porous, granular polymers used as fillers for GPC and for porous Ion exchange resin matrices are used, preferred.

In the patent DE-PS 33 24 835 polymers are reversed Suspension polymerization produced.

In the reverse suspension polymerization, an aqueous solution of the monomers in an inert hydrophobic liquid and suspended in the presence of a lipophilic Protective colloids and an initiator at a corresponding polymerization temperature copolymerized products in pearl form.

In the reverse suspension polymerization, the use of halogen-containing, organic solvents as hydrophobic liquids that form the oil phase. Accordingly, all inert liquids which are immiscible with water can be used, which can be easily separated from the hydrophilic copolymer. Such Liquids are e.g. B. organic solvents, especially hydrocarbons, such as. B. Cyclohexane, n-pentane, n-hexane, n-heptane, i-octane, technical hydrocarbon mixtures, Toluene, xylene and halogenated hydrocarbon mixtures, such as. B. Chlorobenzene or o-dichlorobenzene.

The methods mentioned either describe the preparation of slightly cross-linked styrene Divinylbenzene copolymers (divinylbenzene content up to 17 wt .-%) in a dispersion or Suspension polymerization, in the presence of inert, organic substances (pore regulator) or the representation of hydrophilic, cross-linked polymers in an inverse Suspension polymerization in the presence of halogenated organic substances. In the patents is not involved in the production of chlorine-containing, highly porous adsorber polymers Divinylbenzene content up to 80 wt .-%, in a dispersion or suspension polymerization described.

The aim of the invention results from the prior art.

Aim of the invention

The aim of the invention is a process for the production of chlorine-containing, latently porous Adsorber polymers with a larger surface area and improved adsorptive properties.

State the nature of the invention

The object of the invention is to consist of a mixture of monomers from divinyl benzene (2 to 80% by weight divinyl benzene), ethyl vinyl benzene and others Monomers in a radical dispersion or suspension polymerization in Presence of at least one polymerization initiator and 0.5 to 100 percent by volume, based on the total volume of the monomer mixture, one or more chlorine-containing, organic substances, or a mixture of chlorine-containing organic substances and other inert organic substances to develop a process which the Objective corresponds.

A process was developed which differs from the known processes in that that for the production of highly crosslinked adsorber polymers, there are ways that it allow during the radical polymerization of monomers in the dispersion or Suspension polymerization by adding suitable chlorine-containing organic substances Chloromethylation or chlorination of the polymeric matrix.  

The object is achieved in that the already known method of dispersion or suspension polymerization of a monomer mixture consisting of divinylbenzene (20 to 80 wt .-%), ethylvinylbenzene and other monomers, such as. B.

• - ethylene halide derivatives: vinyl chloride, vinyl bromod, vinyl fluoride, vinylidene chloride, Tetrafluoroethylene, chlorotrifluoroethylene, vinylbenzyl chloride,
• - styrene and styrene derivatives: o-, m- and p-methylstyrene, o-, m- and p-ethylstyrene, o-, m- and p-chlorostyrene, m- and p-bromostyrene, cyanstyrene, o-, m- and p-aminostyrene, Hydroxystyrene
• - vinyl ketone derivatives: methyl vinyl ketone, phenyl vinyl ketone, divinyl ketone, crotonaldehyde, Acrolein, methacrolein, dimethyl ketene
• - Acrylamide and methacrylamide derivatives: acrylamide, N- (1,1-dimethyl-3-oxobuthyl) - acrylanuid, methacrylamide, acrylpiperazine
• - Acrylic and methacrylonitrile derivatives: acrylonitrile, methacrylonitrile
• - divinyl ketone, divinyl ether,
• Diphenylethylene, vinylnaphthalene, vinyltoluene, divinyltoluene, divinylxylene, divinylnaphthalene, Trivinyl benzene, divinyl diphenyl ether, etc.

in the presence of at least one polymerization initiator such as. B. 2,2'-azo-di-isobutyronitrile (AIEN) or dibenzoyl peroxide and 0.5 to 100 volume percent, based on the Volume total of the monomer mixture, one or more chlorine-containing, organic Substances such as B. dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, Trichloroethane, tetrachloroethane, trichlorethylene and tetrachlorethylene, etc. performed becomes.

With the newly developed process, adsorber polymers with specific surfaces over 700 m ² / g could be produced. The adsorption behavior of the adsorber polymers produced in this way is comparable to that of commercially available, highly porous adsorber polymers.

For the first time, the new process opens up the possibility of using chlorine-containing organic substances in the radical dispersion or suspension polymerization of Monomers or monomer mixtures to come to adsorbent polymers, which is a big one specific surface, a high chlorine content in the polymer matrix and pronounced Have adsorption properties against many organic substances, as well as good ones Show osmotic and mechanical stability.

Because of their high chlorine content in the polymer matrix, the new adsorber polymers produced by the process according to the invention can additionally be crosslinked by known processes. The specific surface of the new adsorber polymers can be increased to over 900 m ² / g by the post-crosslinking. Post-crosslinking is not part of the method according to the invention.

The following exemplary embodiments serve to explain the invention without its Restrict claims. All percentages are percentages by weight, unless otherwise specified.  

Embodiments example 1

In a 250 ml sulfonation flask with stirrer, thermometer and reflux condenser, 2.9 g of NaCl and 0.25 g of yeast dissolved in 67 ml of water at 40 ° C. To do this, add one with constant stirring Solution of 1 g AIBN, 13.5 ml carbon tetrachloride and 20 ml monomer mixture.

An 80% solution of divinylbenzene in ethylvinylbenzene is used as the monomer mixture used.

An emulsion of fine monomer droplets in water is obtained, which is obtained if possible constant stirring speed is heated to 70 ° C.

The crosslinking becomes visible after about 1 to 1.5 hours (gelation).

After stirring for 2 hours at 70 ° C, the temperature is raised to 76 ° C.

The mixture is stirred for a further 10 hours at the appropriate temperature and then left under Cool the stirring to room temperature.

The beads are filtered off, the polymer is washed first with water and then, if necessary, with methanol. The washing solution is suctioned off and the polymer is dried in a vacuum drying cabinet at 80 ° C. for 24 hours. The polymer has a chlorine content of 10.7%. The specific surface area of the polymer is 690 m ² / g.

Example 2

As described in Example 1, an adsorber polymer is prepared, but using 150 ml of water instead of 67 ml of water.
The polymer has a chlorine content of 12.1%. The specific surface area of the polymer is 780 m ² / g.

Example 3

As described in Example 1, an adsorber polymer is prepared, but using 40 ml of water instead of 67 ml of water.
The polymer has a chlorine content of 12.8%. The specific surface area of the polymer is 730 m ² / g.

Example 4

As described in Example 2, an adsorber polymer is prepared, but using 0.4 g of AIBN instead of 1 g of AIBN.
The polymer has a chlorine content of 8.3%. The specific surface area of the polymer is 750 m ² / g.

Example 5

As described in Example 1, an adsorber polymer is prepared, but a 60% solution of divinylbenzene in ethylvinylbenzene was used as the monomer mixture instead of the 80% solution of divinylbenzene in ethylvinylbenzene.
The polymer has a chlorine content of 10.0%. The specific surface area of the polymer is 560 m ² / g.

Example 6

As described in Example 5, an adsorber polymer is prepared, but using 40 ml of water instead of 67 ml of water.
The polymer has a chlorine content of 10.7%. The specific surface area of the polymer is 570 m ² / g.

Example 7

As described in Example 2, a polymer is prepared, but instead of 20 ml of an 80% solution of divinylbenzene in ethylvinylbenzene, 1 ml of a 60% solution of divinylbenzene in ethylvinylbenzene and 19 ml of styrene was used as the monomer mixture.
The polymer has a chlorine content of 6.8%. The degree of swelling of the polymer in toluene is 4.9 gTol / gP).

Example 8

As described in Example 2, a polymer is prepared, but instead of 20 ml of an 80% solution of divinylbenzene in ethylvinylbenzene, 2 ml of a 60% solution of divinylbenzene in ethylvinylbenzene and 18 ml of styrene were used as the monomer mixture.
The polymer has a chlorine content of 8.8%. The degree of swelling of the polymer in toluene is 2.7 gTol / gP).

Example 9

As described in Example 2, a polymer is prepared, but instead of 20 ml of an 80% solution of divinylbenzene in ethylvinylbenzene, 3.5 ml of a 60% solution of divinylbenzene in ethylvinylbenzene and 16.5 ml of styrene were used as the monomer mixture.
The polymer has a chlorine content of 11.2%. The degree of swelling of the polymer in toluene is 1.8 gTol / gP).

Example 10

As described in Example 9, a polymer is prepared, but tetrachlorethylene was used as the chlorine-containing organic substance instead of tetra.
The polymer has a chlorine content of 6.0%. The degree of swelling of the polymer in toluene is 2.0 gTol / gP).

Example 11

As described in Example 10, a polymer is prepared, but 5 ml of a 60% solution of divinylbenzene in ethylvinylbenzene and 15 ml of styrene were used as the monomer mixture.
The polymer has a chlorine content of 6.0%. The degree of swelling of the polymer in toluene is 1.4 gTol / gP).

Example 12

As described in Example 8, a polymer is prepared, but using trichlorethylene as the chlorine-containing organic substance instead of tetra.
The polymer has a chlorine content of 9.7%. The degree of swelling of the polymer in toluene is 2.7 gTol / gP).

Example 13

As described in Example 9, a polymer is prepared, but using trichlorethylene as the chlorine-containing organic substance instead of tetra.
The polymer has a chlorine content of 11.7%. The degree of swelling of the polymer in toluene is 1.9 gTol / gP).

Example 14

As described in Example 11, a polymer is prepared, but using trichlorethylene as the chlorine-containing organic substance instead of tetra.
The polymer has a chlorine content of 11.6%. The degree of swelling of the polymer in toluene is 0.8 gTol / gP).

Example 15

As described in Example 14, a polymer is prepared.
The polymer has a chlorine content of 12.4%. The degree of swelling of the polymer in toluene is 0.8 gTol / gP).

Claims (9)

1. The invention relates to a method for producing pearl-shaped, chlorine-containing highly porous adsorber polymers, obtainable by radical polymerization and simultaneous chloromethylation of a mixture consisting of divinylbenzene (2 to 80 Weight percent divinylbenzene), ethylvinylbenzene and other monomers in one Dispersion or suspension polymerization in the presence of at least one initiator and 0.5 to 100 volume percent, based on the total volume of the Monomer mixture, one or more chlorine-containing, organic substances. 2. Adsorber polymers according to claim 1, obtainable in that by radical Polymerization and simultaneous chloromethylation in the dispersion or Monomer mixture used in suspension polymerization, from divinylbenzene (2 to 80 Weight percent divinylbenzene), ethylvinylbenzene and other monomers. 3. Adsorber polymers according to one of claims 1 to 2, obtainable in that the radical polymerization and simultaneous chloromethylation in the dispersion or Suspension polymerization in the presence of 0.5 to 100 percent by volume, based on the total volume of the monomer mixture, one or more chlorine-containing, aliphatic substances with 1 to 12 carbon atoms and 1 to 6 chlorine atoms is carried out. 4. Adsorber polymers according to one of claims 1 to 2, obtainable in that the radical polymerization and simultaneous chloromethylation in the dispersion or Suspension polymerization in the presence of 0.5 to 100 percent by volume, based on the total volume of the monomer mixture, one or more chlorine-containing Cycloalkanes with 6 to 12 carbon atoms and 1 to 6 chlorine atoms is carried out. 5. Adsorber polymers according to one of claims 1 to 2, obtainable in that the radical polymerization and simultaneous chloromethylation in the dispersion or Suspension polymerization in the presence of 0.5 to 100 percent by volume, based on the total volume of the monomer mixture, one or more chlorine-containing, aromatic substances with 6 to 24 carbon atoms and 1 to 12 chlorine atoms is carried out. 6. Adsorber polymers according to one of claims 1 to 2, obtainable in that the radical polymerization and simultaneous chloromethylation in the dispersion or Suspension polymerization in the presence of 0.5 to 100 percent by volume, based on the total volume of the monomer mixture, one or more chlorine-containing, aliphatic unsaturated substances with 1 to 3 double bonds and / or 1 to 3 Triple bonds in the molecule, 1 to 12 carbon atoms and 1 to 6 chlorine atoms is carried out. 7. Adsorber polymers according to one of claims 1 to 2, obtainable in that the radical polymerization and simultaneous chloromethylation in the dispersion or Suspension polymerization in the presence of 0.5 to 100 percent by volume, based on the total volume of the monomer mixture, one or more chlorine-containing, cyclic, unsaturated substances with 1 to 3 double bonds and / or 1 to 3 Triple bonds in the molecule, 6 to 12 carbon atoms and 1 to 6 chlorine atoms is carried out. 8. Adsorber polymers according to one of claims 1 to 2, obtainable in that the radical polymerization and simultaneous chloromethylation in the dispersion or Suspension polymerization in the presence of 0.5 to 100 percent by volume, based on the total volume of the monomer mixture, a mixture of chlorine-containing, organic Substances is produced, defined in more detail in claims 3 to 7.   9. Adsorber polymers according to one of claims 1 to 2, obtainable in that the radical polymerization and simultaneous chloromethylation in the dispersion or Suspension polymerization in the presence of 0.5 to 100 percent by volume, based on the total volume of the monomer mixture, a mixture of chlorine-containing, organic Substances, defined in more detail in claims 3 to 7, and other organic Substances is produced.