DE2531101A1 - MACROMOLECULAR SUBSTANCES WITH SATURATED C-CHAINS AND THEIR PRODUCTION AND USE - Google Patents

Description

The invention relates to new macromolecules with saturated, bifunctional C chains, and their production process and their use, especially in the treatment of industrial wastewater.

The treatment of industrial wastewater, especially phenol-containing wastewater from paper mills and refineries or the like, enjoys considerable interest today; the treatment Such wastewater is also necessary because the legislation has very strict limit values for impurities are fixed.

The current treatment methods, for example for waste water containing phenolic substances, are based on the breakdown of phenol (photochemical breakdown, specific biological treatment, ozonization) or on the recovery of phenol by adsorption,

097- (AN2-BE 255-Cas 7) -SFBk

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Extraction or evaporation.

The processes of phenol degradation generally have the disadvantage that, due to the degradation products, they in turn Represent impurities, a secondary impurity occurs; in addition, such degradation processes do not work profitably as they do not result in any recovery.

In the previously specified processes for the recovery of phenols by adsorption, products with a large specific surface such as activated carbon, silica gel or the like. used, the regeneration of which is difficult and at the same time lead to a relatively low adsorptive yield to lead.

(■ '■''-' ■■ '■ ' ■ ' ' · ■■■■■ · ■ ^: ■■■■■ .- ■ ■ In the extraction processes in which solvents are used, the yields are equally low; such methods also require expensive facilities, making them uneconomical.

The evaporation processes are finally with associated with a b ^ deuterid energy consumption.

The invention is based on the object of specifying new macromolecular substances with which it is particularly possible, while avoiding the above Disadvantages of treating aqueous waste water containing phenol perform; a manufacturing process for the macromolecular substances should also be specified will.

The macromolecular substances according to the invention

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have the following formula:

Λ.

R.

\ J

C = ■ Y

in it mean:

Rp and R, at least divalent groups, R, R and Uu monovalent substituents and X and Y heteroatoms or groups of atoms.

The hetero atom Y can be oxygen through which the macromolecule has a carbonyl function. The substituents Rp and R (- are in particular methylene groups, the Substituent R- * is a methyl group. X can be a halogen atom (chlorine, bromine or the like.) Or a nitrogen-containing or represent a hydroxyl group. The groups R, and R ^ can also consist of hydrogen.

If X represents a halogen and Y represents oxygen, the manufacturing process of the macromolecular substance consists in the polymerization of a conjugated diene to a polyalkene and in the reaction with an oc ~ halo ketone in the presence of a Lewis acid.

According to a first embodiment of the invention Procedure, the addition reaction is carried out in a halo-

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carried out generated solvent in which the polyalkene is completely soluble, which increases the yield of the addition.

According to a second way of carrying out the method according to the invention, in which adsorbed onto a carrier Macromolecules are obtained, the polyalkene produced is in a solvent, in particular a halogenated one Solvent dissolvedj the solution is then dissolved poured the selected support and allowed to evaporate, thereby depositing the polyalkene on the support. Of the Carrier can, for example, made of silica gel, activated carbon or the like. exist. In a third stage, the ot-halo ketone is used added in the presence of the Lewis acid to the polyalkene applied to the support.

The products obtained by the two exemplary implementation methods can be used as 'poly-ß-haiogenketones' are designated.

When X is a heteroatom other than a halogen represents, a macromolecule with a halogen X 'is previously prepared by the method described above, after which the halogen X 'is replaced by the heteroatom X of a different type; this last step is by nucleophilic substitution, in particular in an aqueous medium.

Experimental studies have shown that the invention Macromolecular substances have the property of phenols with remarkable effectiveness to tie. These properties are probably based on the one hand on the presence of the double bond C = Y, opening of which enables an addition reaction of the phenols, as well as on the other hand on the tendency of

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Macromolecules, chelates between the acidic hydrogen the phenols and the heteroatoms or groups of atoms X and Y train.

The method according to the invention for treating waste water with phenolic compounds is based accordingly on bringing the wastewater into contact with the macromolecules either free or adsorbed on a carrier to bind the phenols on this; the bringing together can, for example, by passing the sewage through be made by a bed of the macromolecular substance.

The table below shows the percentages of phenol bound after 1 hour and a single pass for a given amount of the macromolecular substance as a function of the concentration of phenol specified in wastewater; the example refers to the following macromolecular substance (acetylated polybutadiene) :

* ~ Cl

CH

₂ \

C = O

Phenol concentration in wastewater

% bound phenol

Amount of macromolecular substance based on the wastewater volume ι

10 g / l

5 SAT
25 %

3 g / l 36 %

1 g / l

0.5 g / l

42

o, igA

0.66 g / 200 ml solution

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Taking into account the minimum amount of used macromolecular substance is apparent from the test results that the amount of bound phenol is remarkable is higher, especially in the area of higher concentrations than in conventional adsorption processes.

In practice, an excess is used to achieve as complete a bond as possible to the phenol the macromolecular substance used and the solution enforced several times.

The bound phenolic compounds can be recovered by treatment with alkali, through which the bond between macromolecule and phenol is broken.

The macromolecular substances according to the invention can also be used to purify waste water which contain positive ions, especially heavy metal ions or transition metal ions.

The process consists in a simple manner in the solution of the positive from the sewage Bringing ions together with the macromolecular substance, for example, as a fixed bed in a In this way, the positive ions are complexed by the Makromolekttl, which enables the ions to be separated from the solution.

The macromolecular substances according to the invention in which the heteroatom Y represents an oxygen atom, can also covalently bond a compound with an NH bond (for example primary or secondary amines) be used; to carry out this bond, the compound is in an anhydrous medium with the macromolecular

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ular substance brought together and the resulting Water removed.

The binding reaction is preferably carried out in anhydrous benzeneic medium and the removal of the water made by azeotropic distillation.

The bonding process mentioned is particularly useful for separating amines with an NH bond (primary or secondary amines) of non-acidic compounds applicable; the amine becomes selectively in anhydrous liquid Phase bound, the non-acidic (unbound) compound remaining in the liquid phase; the liquid The phase is then separated on the solid phase, which is hydrolyzed to obtain the amine regenerated in this way can be.

The non-acidic compound can in particular consist of a tertiary amine, which in this way of primary and secondary amines can be separated. This possibility is extremely practical Interest, since the production of amines generally results in mixtures of primary, secondary and tertiary amines leads, the separation of which is accordingly an important requirement.

The invention is not restricted to the exemplary modes of implementation given; others too suitable modes of implementation are contained in the general inventive concept.

The macromolecular substances according to the invention can bind phenolic 'compounds, more positive Ions or of compounds with NH bonds are used «

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Claims (1)

Claims 1. Macromolecular substance of structure C = Y where mean} .R ₁ Rr and Rf- at least divalent groups, R-., R, and Rjj, monovalent substituents as well X and Y are heteroatoms or groups of atoms. 2. Macromolecular substance according to claim 1, characterized in that that the hetero atom Y represents an oxygen atom, so the macromolecule carbonyl functions having. J5. Macromolecular substance according to Claim 1 or 2, characterized in that the substituents Rp and Rj. Represent methylene groups -CH ₂ -. 4. Macromolecular substance according to any one of claims 1-5 »daduroh characterized in that the substituent R, a methyl group © represents. 509884/1166 5. Macromolecular substance according to any one of claims 1-4, characterized in that the hetero atom y is a halogen atom is. 6. Macromolecular substance according to any one of claims 1-5, characterized by the following structure -CH. Cl i
C. CH ₂ "
H CH Process for the production of the macromolecular substance according to claims 2-5, characterized by polymerization a conjugated diene to a polyalkene and its reaction with an od-halo ketone in the presence a Lewis acid. 8. The method according to claim 7, characterized in that the addition reaction in a halogenated solvent is carried out. 9. The method according to claim 8 for producing a macromolecular substance adsorbed on a carrier, characterized in that that the polyalkene dissolved after its preparation in a solvent and the solution to a The carrier is poured and allowed to evaporate to produce a deposit of the polyalkylene on the carrier, followed by evaporation the oc-haloketone in the presence of a Lewis acid is added. 509884/1166 10. Process for the treatment of waste water containing phenolic substances for the purification and removal of the phenolic compounds, characterized in that macromolecular substances according to claim 1 for binding the phenolic compounds on the macromolecules are brought together with the wastewater. 11. The method according to claim 10, characterized in that the wastewater through a bed of the macromolecular Substance is passed through. E0SM4 / 11C