DE2439932A1 - THREE-DIMENSIONAL GEL-LIKE MATERIALS CONTAINING THREE-DIMENSIONAL GEL-LIKE MATERIALS AND THEIR MANUFACTURING PROCESS - Google Patents

Description

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PATENT ADVOCATE.

October 14, 1974 file .; P 24 39 932. 4 application files: 75,738

PATEITlJl EL D ti Φ & ν- ^;

Applicant; Geskoslovenska akademie v§d., Praha 1

C * S.S.R.

Title; Three-dimensional gel-like materials containing dissociable residues of phosphoric acid and their manufacturing process

The invention relates to organic gel-like materials which are crosslinked by chemical cross-links and which contain covalently bound phosphoric acid Molecules retain acidic character which they can dissociate into the first or second stage and which are characterized by properties of ion exchangers.

Polymers are made by copolymerization in a suspension of derivatives of acrylic or methacrylic acid,

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which contain one or more hydroxyl or epoxy groups, with crosslinking comonomers in the molecule contain two or more copolymerizable double bonds, for example of the acryloyl or methacryloyl type, or with divinylbenzene and subsequent reaction of the resulting three-dimensional polymers, which contain free hydroxyl or epoxy groups with phosphoric acid or its derivatives. Next to homogeneously crosslinked gels can also be produced under well reproducible reaction conditions, heterogeneous gels, which is characterized by constant porosity, even when dry, by well-defined distribution the pore size and are characterized by a considerable internal surface. These properties confer the gel-like materials a satisfactory exchange capacity of the superficially bound functional groups.

The materials produced in this way can preferably be used as strong base exchangers in separation processes in ion exchange chromatography, as use effective catalysts of some chemical reaction and finally as polymeric reagents which take advantage of the reactivity of chemically bound phosphoric acid, possibly also of its halogen derivatives.

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As is known, there are many ion exchangers with acidic functional groups which .ge- on organic polymers. be bound. Copolymers of styrene and divinylbenzene are predominantly used as the carrier Exchange groups then the suIfogruppen -S $ xH «copolymers of styrene-divinylbenzene are in the majority homogeneous and characterized by a three-dimensional structure with a low density of cross-bonds, see above that they swell due to the action of solvents. Macroporous structures are achieved by interpolymerization with a higher amount of the. Crosslinking agent, in the presence of inert solvents with various solvation capacities for polymer.

According to this invention, strongly acidic cation exchangers can be obtained by chemical fixation of phosphoric acid molecules to a copolymeric matrix by the chemical reaction of a previously prepared gel with phosphoric acid or its derivatives, the ability of phosphoric acid or its derivatives to react with hydroxyl or epoxy groups which are present in the gel ^", are, by exploits From the Anwendung'hör sailed heritable preferably one makroporäse gels which sogar'im dry state, by a measurable, beständige'Porosität and large internal surface area where the Binduiigöreaktiönverläuft distinguished, and which. their properties

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allow easy access of the reacting components to the acidic functional group. this fact includes the use of homogeneous, thinly crosslinked, phosphorylation modified gels for some Processes in the low molecular area, such as ion exchange, acid catalysis of organic reactions and the like, not off.

The term "carrier" is understood to mean a defined, polymeric material which is produced by copolymerizing esters of the Acrylic or methacrylic acid, which contain one or more hydroxyl functional groups, for example from Hydroxyalkyl acrylates, hydroxyalkyl- hydroxyalkyl methacrylates, oligo- or polyglycol acrylates, oligo- or Polyglycol methacrylates, of derivatives of acrylic or methacrylic acid, which contain epoxy groups, e.g. glycidyl acrylates, glycidyl methacrylates with cross-linked divinylbenzene or polyvinylic monomers, e.g. with alkylene diacrylates, alkylene dimethacrylates, Oligo- or polyglycol diacrylates, oligo- or polyglycol dimethacrylates, with two or more times acryloylated or methacryloylated polyfunctional alcohols or alcoholic sugars, if appropriate with divinylbenzene.

For the polarity regulation of the gel material, its

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certain affinity to the solvent or to the solute Compound represents the condition for the course of the reaction with bound phosphoric acid, one can ternary copolymerization with more or less polar monomers such as styrene, alkyl methacrylates and acrylates, Acrylonitrile, acryloylmorpholine, substituted acrylamides and methacrylamides and the like. The necessary condition which must be met when selecting the third comonomer is its sufficient thermal and hydrolytic resistance for incorporation into the copolymer matrix Reaction conditions for the binding of the phosphoric acid and under the conditions of further cation exchange use.

The binding of the phosphoric acid is carried out in such a way that that one reacts free hydroxyl or epoxy groups in the gel under suitable conditions with phosphorus compounds lets which either directly (EzP (L) or after the Hydrolysis (POCl ^, P20c, PClv) mass with chemically bound Phosphoric acid molecules capable of dissociating into the first or second stage. Spruce hydrolyzed products of the reaction of the gels with phosphorus oxychloride can be considered highly reactive polymers Reagents for binding compounds containing hydroxyl groups, for example alcohols, sugars,

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, Nucleic acids and _# ä., Using nucleotides. In these reactions, the compounds listed are bound to the G-el by ester groups.

Phosphoric acid chemically bound to a polymer matrix can also contain various coordination compounds form for practical application. In the heating of completely dried phospholyzed gel with Complex acids are formed from gaseous boron trifluoride

( ^Bi Vx> which can be used with advantage as an effective catalyst

The invention is further explained in more detail by means of examples, without being restricted to these. Parts and percentages in the examples are, unless expressly stated otherwise, as parts by weight and expressed as percentages by weight.

example 1

100 parts of macroporous copolymer of 2-hydroxyethyl methacrylate with ethylene dimethacrylate with a precipitation limit of 300,000 units of the molecular weight and a specific surface area of 77 m / g, particle size 200-300 µm were placed in sulfonation flasks

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suspended in 300 parts of dry benzene with 75 parts of triethylamine. At a temperature of 0 - 5 ⁰ G was gradually added under stirring so effective that the temperature of the reaction mixture did not exceed the defined area 100 parts of phosphorus oxychloride (POCl *). After the addition of all the phosphorus oxychloride, the mixture was stirred at a temperature of 10 ⁰ C within 2 hours and allowed to stand "at a temperature of 5 ° C within 12 hours, The gel suspension was then separated by filtration from the liquid, with 100 Parts of chloroform washed completely three times and dried in vacuo. The non-hydrolyzed group containing -OP-Clp

Part of the dry gel was allowed to react with alcohol (see example 10). ...-..-.

The hydrolysis was carried out in stages by using the dry gel (100 parts) in 2000 parts of 10 ^: f ° solution of NaHCO ^ with intensive development

carried out by carbon dioxide. After adding the whole Geled into the sodium hydrogen carbonate solution, the mixture was allowed to stand at room temperature. The gel was then used ten times with 200 parts each Distilling water washed through, in the It cycle by three times Wash through with 1000 parts of 5 $ HCl each

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transferred, washed through again five times with 200 parts of distilled water each time (until a neutral reaction) and dried out on the filter after the last wash with acetone and ether. The product obtained was titrated potentiometrically with 0.1 N solution of NaOH and had an exchange capacity of 2.2 meq / g.

Example 2

A cation exchanger with an exchange capacity of 2.35 meq / g was prepared in a manner similar to that in Example 1 produced with the difference that the carrier is a macroporous copolymer of triethylene glycol monomethacrylate with ethylene dimethacrylate with a precipitation limit of the molecular weight of 10000 was used.

Example 3

A phosphorylated cation exchanger with an exchange capacity of 1.98 meq / g was produced in a manner similar to Example 2 with the difference that copolymer of 2-hydroxyethyl methacrylate with methyl methacrylate and ethylene dimethacrylate having an exchange limit of 500,000 molecular weight was used as the carrier.

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Example 4

A phospholyzed cation exchanger was prepared similarly to Example 1 with the difference that a copolymer of diethylene glycol dimethacrylate, diethylene glycol monomethacrylate and acrylamide as a carrier was used · The excretion limit of the carrier was 50 QOO, the exchange capacity of the cation exchanger was 1.34 meq / g.

Example 5

Suspended copolymer (1 part) of styrene, and GIycidylmethacrylat Diviny! Benzene containing 27.3 1 »GIycidylmethacrylat was swollen in 20 parts of dry toluene, and with stirring 2.5 parts of phosphorus pentoxide were of at a temperature of 11O ⁰ C during boiling Solvent added under the reflux condenser. After 15 hours of reaction, the product was washed through with 20 parts of ethanol, 20 parts of water and again with 10 parts of ethanol. After the filtered gel suspension had dried out, the content of bound phosphoric acid (23.4 1 °) was determined *

Example 6 ■

Part of the suspension described in Example 5

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Copolymers were treated in a manner similar to that in Example 5 with 3.5 parts of 35% phosphoric acid over the course of 24 hours. The end product was processed in the same way as in Example 5. The bound phosphoric acid content was 17.5 °.

Example 7

Part of the macroporous copolymer of 2-hydroethyl methacrylate was with ethylene dimethacrylate with a precipitation limit of the molecular weight of Phosphorus pentoxide was added to 300,000 in a manner similar to that in Example 5. After the product had been washed through, was the exchange capacity by potentiometric titration of the cation exchanger (0.713 meq / g) determined.

Example 8

Part of the macroporous copolymer of 2-hydroxyethyl methacrylate was with ethylene dimethacrylate with a precipitation limit of the molecular weight of 300,000 with $ 85 phosphoric acid under the conditions of example 6 offset. The exchange capacity of the product obtained was 1.84 meq / g.

Example 9

7 parts of a similar way as in example 1

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Cation exchangers were placed in the flask, which was equipped with a gas supply tube and a thermoelectric !! Thermometer was provided, used. Under external cooling with ice, gel in the dry state with BF _x

and nitrogen at a rate such barboiiert that the registered by the thermocouple temperature did not exceed 6O ⁰ G. After the development of the heat of reaction had ceased, the gel was baroped with nitrogen within 15 minutes in order to remove adsorbed unplaced boron bifluoride. The mass increase was on the balance of the product 32 f "and changed either by further washing through gel particles with nitrogen, or by evacuation. The complex of phosphoric acid with boron trifluoride bound to the gel matrix has been used as an effective catalyst for ¹ Friedel-Craft reactions, and when Polymerisationsauslösen of styrene and ethylene oxide.

Example 10

10 parts of the non-hydrolyzed product from Example 1 were dissolved in benzene (100 parts) at 80.degree heated within 4 hours with 10 parts of lauryl alcohol. From the increase in mass and the elemental analysis it was found that the esterification of free hydroxyl groups of the phosphoric acid bound to the gel was complete was.

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Example 11

The production of a cation exchanger with an exchange capacity of 1.92 meq / g was carried out in a manner analogous to that in Example 1 carried out with the difference that instead of phosphorus oxychloride the same amount of phosphorus pentoxide was used to manufacture.

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Claims (1)

PATENT CLAIMS: 1. Three-dimensional gel materials, which contain dissociable residues of phosphoric acid, its halogen derivatives or their complexes with strong Lewis acids, such as BF ^, AlCl ,, - by ester bond to Bound carrier - contain which copolymers of hydroxy esters or epoxy esters of acrylic or Methacrylic acid with crosslinking monomers which have two or more copolymerizable polymers in the molecule Contain double bonds, form » J A process for the production of materials with covalently bound phosphoric acid or its derivatives according to claim 1, characterized in that the carrier substance of the gel is added by copolymerization of the monomers mentioned in claim 1 with phosphoric acid, phosphorus oxyhalides, phosphorus pentoxyhalides or with phosphorus pentoxide of halides or oxyhalides subjects the product obtained to a subsequent hydrolysis by water or weak alkalis, the result of which is the substitution of halogens for the phosphoric acid bound in the molecule - 14 - 50981 1/0992 _ 14 - 3. The method according to claim 2, characterized in that the halides of phosphoric acid, Form phosphorus pentachloride or bromide and phosphorus oxychloride or bromide, 4. The method according to claim 2, characterized in that there is a reaction with phosphoric acid and their derivatives listed in claims 2 and 3 macroporous, by copolymerization of the Monomers according to Claim 1, in the presence of liquids, the monomers dissolve, but the copolymer formed felling, manufactured carrier substance used. 5. The method according to claim 2, characterized in that one for binding phosphoric acid and their derivatives used gel-like carriers, which by ternary copolymerization of the monomers recited in claim 1 which decrease or increase the polarity of the carrier, e.g. Styrene, alkyl acrylates, alkyl methacrylates, acrylonitrile, methacrylonitrile, acrylamides, methacrylamides and Acryloylmorpholine, is produced «, 50981 1/0992