CA1081395A - Polymers containing a reactive aromatic system and method for their preparation - Google Patents
Polymers containing a reactive aromatic system and method for their preparationInfo
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- CA1081395A CA1081395A CA329,601A CA329601A CA1081395A CA 1081395 A CA1081395 A CA 1081395A CA 329601 A CA329601 A CA 329601A CA 1081395 A CA1081395 A CA 1081395A
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Abstract
ABSTRACT OF THE DISCLOSURE:
The invention is concerned with polymers containing structural units of the general formula:
The invention is concerned with polymers containing structural units of the general formula:
Description
This application is a division of application No. 241,036 filed December 4, 1975.
Efforts to prepare new kinds of polymers with built-in functional groups, which enable chemical modifications of the polymeric system, lead to syntheses of numerous compounds having the character of monomers. The invention relates to synthetic polymers which contain in the side chain a p-phenylenediamine skeleton enabling manifold chemical modifications of the system, and to a method for their preparation. l`he aim is to prepare materials suitable for subsequent application, e.g. as a catalyst of chemical reaction, biologically active preparation, ion exchanger, and the like, by a simple subsequent reaction of the polymers.
Interest in polymers with reactive functional groups, which are raw materials for numerous products of both technological and application importance, caused the rapid development of modified polymeric systems. These polymers are prepared by modification of the fundamental polymeric skeleton by a subsequent chemical reaction, on the one hand, and by copolymerization of suitable monomers with reactive groups capable of further reactions, on the other.
Polymers preformed in this way may be transformed by further chemical conversions into materials useful for biological applications, technical applications, and the like.
Théy were developed materials containing an aliphatic or aromatic primary amino group in the side chain which may be used, for example, for further reactions of the bonding character via diazotizing of the aromatic amino group and the subsequent coupling with a suitable kind of substrate. However, most of these systems prefer the one-sided utilization. In addition to it, several reactions provide imperfectly defined products because the modification reactions are not quantitative or the corresponding comonomers have unsuitable reactivity ratios.
: - . . .
-` ~0~31395 The parent application proposed to provide monomers containing a p-phenylenediamine skeleton and having the general formula:
CH2 f Co-(o-cH2-cH2)x-N-Ar-NH-R3 (I) Rl R2 wherein Rl ishydrogen or a methyl group, R2 is an alkyl or hydroxyalkyl containing 1 to 6 carbon atoms, R3 is an acyl, sulfate or hydrochloric group, Ar is p-phenylene, and x is 1 to 4.
The above acrylate esters are prepared in accordance with the invention of the parent application by blocking the free primary amino group of an aromatic diamine having the general formula:
H ( CH2 CH2)x ~N Ar NH2 (II) in which R2, Ar and x have the aforesaid meanings, to form an -NH-R3 group in which R is an acyl, sulfate or hydrochloride group, and reacting the resulting blocked diamine with an acryloyl or methacryloyl halide.
The starting aromatic diamine may be obtained by reacting ethylene oxide with an N-alkyl aniline, nitrosating the resulting N-hydroxyethylated N-alkyl aniline, and reducing the resulting p-nitroso-N-hydroxy-ethylated N-alkyl aniline. The reaction of the blocked diamine with the acryloyl or methacryloyl halide is preferable carried out in anhydrous pyridine to 5C for 1 hour and at 25-30C for 10 hours, and the acrylate ester thus produced is recovered by crystallization.
The acrylate esters described in the parent application are noted for their suitable copolymerization reactivity ratios .: . . . . . . . . :................ .
: ,:: . ~ : -: . . . - .
~Ol~3g5 with common monomers. They can be prepared as mono- or bifunctional monomers at the same time and, consequently, used for preparation of linear polymers soluble in proper solvents and insoluble crosslinked polymers.
The present divisional application is directed to polymers containing structural units of the general formula:
I / R
-cH2-f-co-(o-cH2-cH2)x-l-Ar-N (III) Rl R2 R5 wherein Rl is hydrogen or a methyl group, R is an alkyl or hydroxyalkyl containing 1 to 6 carbon atoms, R4 and R5 are the same or different and represent hydrogen, an acyl, sulfate or hydrochloric group, an alkyl containing 1 to 4 carbon atoms or a -CH2COOH group,with the proviso that R can represent an acyl, sulfate or hydrochloric group only when R4 is hydrogen, or R4 and R5 together with the nitrogen atom to which they are attached form a diazo group, Ar is p-phenylene, and x is 1 to 4.
Polymers of the above formula (III) in which R is hydrogen and ~5 is an acyl, sulfate or hydrochloric group, are prepared by a free-radical polymerization of the corresponding monomer of the formula~ (I) in the presence of an initiator of free-radical polymerization at or above the decomposition temperature of the initiator.
According to a preferred embodiment, the polymerization is carried out in the presence of comonomers consisting of monomers of the acrylic or methacrylic series, such as acrylamide, methacrylamide, acrylic acid, methacrylic acid and their esters, or of vinyl compounds, such as butadiene, isoprene and styrene.
- .
.
The polymerization is advantageously carried out in the presence of polymer solvents and precipitants or in a dispersion medium under formation of porous polymer particles having large inner surface area.
The invention enables to prepare a polymeric system, the chemical reactivity of which given by the conjugated nitrogen system allows to perform several reactions leading to products with specific properties. With respect to advantageous copolymerization reactivity ratios, especially with acrylates and methacrylates, materials of the defined structure with high content of reactive groups may be prepared. The copolymers may be indeed prepared also with other types of monomers, as with styrene, divinylbenzene and their derivatives, isoprene, butadiene, and the like.
The character of the reactive system prefers namely copolymerizations with monomers of hydrophilic nature, e.g. with esters containing hydroxyl group in the side chain, i.e. esters j of glycols, polyglycols or glycerol, with amides, i.e. acrylamide, methacrylamide, or N-substituted acrylamides and methacrylamides, and naturally, with methacrylic and acrylic acids.
The preparation of copolymers in the form of a three-dimensional network by copolymerization with multifunctional monomers, as for instance with divinylbenzene, ethylene glycol dimethacrylate or methylenebisacrylamide, leads to insoluble homogeneous or heterogeneous copolymers. In the presence of a suitable solvent system, polymers with large inner surface area and porosity are formed, which properties predetermine these ma-terials for broad application, namely those prepared in the form of small spherical particles for chromatographic and catalytic purposes and for ion exchange.
Polymers performed in this way may be transformed by further chemical conversions into materials useful for biological and technical applications.
Thus, polymers of the formula (III) in which R4 and R5 are hydrogen, alkyl containing 1 to 4 carbon atoms or -CH2COOI~
group, or R4 and R5 together with the nitrogen atom to they are attached form a diazo group, can be prepared by subjecting a preformed polymer of the formula (III) in which R4 is hydrogen and R5 is an acyl, sulfate or hydrochloric group to an acid hydrolysis and subjecting the resulting product to diazotization, alkylation or reaction with chloroacetic acid.
The reactive site is, for example, a primary aromatic amino group which may be diazotized and used in coupling reactions with various components.
Alkylation of the primary amino group may be carried out, for example, by reaction with formaldehyde (see Example 9) and leads to an aromatic tertiary alkylamine built into the polymeric skeleton.
The formation of a polymeric derivative of aminodiacetic acid is effected by reaction of the polymer with chloroacetic acid.
Polymers according to the invention may be advantageously used as ion exchangers, catalysts of chemical reactions and for biological applications.
The synthesis of monomers and polymers containing a p-phenylènediamine skeleton according to the inventions in the parent and divisional applications will now be further illustrated with reference to the following non-restrictive examples.
Example 1 N-Ethyl-N-(2-hydroxyethyl)-p-phenylenediamine (560 g) is dissolved in 2 1. of water at 45C, 230 g of acetanhydride is added under stirring and the mixture is neutralized with sodium hydroxide to the alkaline reaction (pH - 9). After dilution with three volumes of water, a crystalline product (m.p. 133C) is . . .... - . . . .
~ ,` 1081395 ; obtained, which is further reacted with methacryloyl chloride (10% excess) in the medium of anhydrous pyridine. Methacryloyl chloride is added into the reaction mixture at 5C within one hour and the temperature is then maintained at 25-30C under stirring for 10 hr. After dilution with 5 volumes of water, the oil separates which gives by crystallization from toluene and ethanol-water mixture the crystalline product (m.p. 93-94C).
Example 2 The monomer is prepared according to Example 1, with the distinction that acetate, sulfate or hydrochloride of N-ethyl-N-(2-hydroxyethyl)-p-phenylenediamine is used as the starting material and allowed to react with methacryloyl chloride according to Example 1.
Example 3 .
N-Ethylaniline (0.5 mole) is mixed with 0.6 mole of ethylene oxide in an autoclave, which is then sealed, pressurized with nitrogen to 30 atm and heated up to 130C within 2 hr.
Ethoxyethylated product is obtained in the yield of 95% related to the starting N-ethylaniline. This product is subjected to nitrosation at the temperature 5C with sodium nitrite solution, then reduced with tin in hydrochloric acid and, eventually, subjected to the methacrylation process according to Example 1.
Example 4 N-Ethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine (5 g) is dissolved in 10 g of Methylcellosolve and 0.01 g of azobisisobutyronitrile is added. The mixture is flushed with nitrogen and polymerized at 60C. The resulting polymer solution is diluted and precipitated into ether. The polymer is soluble inMethylcellosolve*,acetone and diluted hydrochloric acid.
* Trademark ~.' ' .
-` 1081395 Example 5 _ N-Ethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine (2.6 g) is mixed with 2.7 g of ethylene glycol monomethacrylate and 0.1 g of azobisisobutyronitrile.
Polymerization at 50 C gives a hard glossy material.
_xample 6 N-Ethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine (1 g) is dissolved in 4 g of methyl methacrylate and 1.3 wt. % of azobisisobutyronitrile is added. The mixture is sealed in an ampoule under nitrogen and gives after polymerization at 50C for 10 hours a glassy polymeric plug.
Example 7 N-Hydroxyethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine (1.5 g) is dissolved in 4.5 g of ethylene glycol monomethacrylate and 0.006 g (i.e., 0.1 wt. ~) of azo-bisisobutyronitrile is added. The mixture is transferred into a polymerization mold formed by two planparallel plates. The polymer resulting after polymerization at 60C for 8hrhas a form of a homogeneous plate.
_xample 8 A polymerization mixture consisting of 31.9 g of ethylene glycol dimethacrylate, 29.4 g of ethylene glycol mono-me-thacrylate, 20.4 g of N-ethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine and 0.82 g (1 wt. %) on monomers of azobisisobutyronitrile is polymérized with addition of 98.5 g of cyclohexanol and 9.7 g of dodecanol in a medium consisting of 600 g of watèr and 6 g of polyvinylpyrrolidone in a reactor at the temperature 50C for 2 hr and at 65C for further 8 hr.
Porous gel particles are obtained which exhibit the specific surface area 150 m2/g.
~081395 Example 9 The polymer prepared by the procedure described in Example 8 (5 g) was subjected to acid hydrolysis in diluted hydrochloric acid (l : l) by boiling for 30 min. This gel is mixed with 50 ml of 98% formic acid and 2 ml of 37% aqueous solution of formaldehyde is added under cooling. After 1 hr of stirring at the ambient temperature, the mixture is boiled (at 100 C) for 24 hr. The resulting gel - alkylated product - is washed with water and ethanol and dried.
Example 10 Diazotizing and coupling with 2-naphtol-3,6-sulfonic acid.
Diazotizing. The gel prepared by the procedure described in Example 8 and subjected to the acid hydrolysis described in Example 9 was washed and afterwards dispersed in hydrochloric acid 1 : 2. The suspension is cooled to -10C and a 10% solution of sodium nitrite is added under vigorous stirring within l hr in a 1.5 fold amount on NH2 groups of the polymer. After addition of the whole amount, the mixture is stirred at the same temperature for another 15 min. The gel is then filtered and thoroughly washed with water and five times with 0.5N HCl.
Coupling. An aqueous solution of 2-naphtol-3,6-sulfonic acid is poured into the filtered gel at 5C; -the resulting mixture has pH 1.5 - 2. The mixture is alkalized with borax under stirring;
coupling takes place at pH 7 , 8 which exhibits itself by turning the gel black the mixture is stirred for another 5 hr. On completion of the reaction, the gel is thoroughly washed with water, lN KOH, water lN H2SO4, water, and ethanol alternatively as long as the washing liquid is no longer colored.
The product is dried from ethanol and characterized by the amount of SO3H groups in the polymer.
` 1081395 _xample 11 Reaction with chloroacetic acid The gel after acid hydrolysis which was washed until the washing water was neutral is dispersed in a solution of sodium chloroacetate and sodium carbonate (1 mole of chloro-acetate and 0.5 mole of carbonate, the solution saturated at 70C). Twenty fold excess of chloroacetate on amount of NH2 groups is used. The mixture is stirred in an inert atmosphere at 95C for 8 hr. After cooling, the gel is filtered and thoroughly washed with lN HCl and water and dried from ethanol.
The product is characterized by the presence of functional groups / CH2-COOH in the polymer.
-N
g ~:
:
_ ........... . - ~ .
- : , . : ' . ,
Efforts to prepare new kinds of polymers with built-in functional groups, which enable chemical modifications of the polymeric system, lead to syntheses of numerous compounds having the character of monomers. The invention relates to synthetic polymers which contain in the side chain a p-phenylenediamine skeleton enabling manifold chemical modifications of the system, and to a method for their preparation. l`he aim is to prepare materials suitable for subsequent application, e.g. as a catalyst of chemical reaction, biologically active preparation, ion exchanger, and the like, by a simple subsequent reaction of the polymers.
Interest in polymers with reactive functional groups, which are raw materials for numerous products of both technological and application importance, caused the rapid development of modified polymeric systems. These polymers are prepared by modification of the fundamental polymeric skeleton by a subsequent chemical reaction, on the one hand, and by copolymerization of suitable monomers with reactive groups capable of further reactions, on the other.
Polymers preformed in this way may be transformed by further chemical conversions into materials useful for biological applications, technical applications, and the like.
Théy were developed materials containing an aliphatic or aromatic primary amino group in the side chain which may be used, for example, for further reactions of the bonding character via diazotizing of the aromatic amino group and the subsequent coupling with a suitable kind of substrate. However, most of these systems prefer the one-sided utilization. In addition to it, several reactions provide imperfectly defined products because the modification reactions are not quantitative or the corresponding comonomers have unsuitable reactivity ratios.
: - . . .
-` ~0~31395 The parent application proposed to provide monomers containing a p-phenylenediamine skeleton and having the general formula:
CH2 f Co-(o-cH2-cH2)x-N-Ar-NH-R3 (I) Rl R2 wherein Rl ishydrogen or a methyl group, R2 is an alkyl or hydroxyalkyl containing 1 to 6 carbon atoms, R3 is an acyl, sulfate or hydrochloric group, Ar is p-phenylene, and x is 1 to 4.
The above acrylate esters are prepared in accordance with the invention of the parent application by blocking the free primary amino group of an aromatic diamine having the general formula:
H ( CH2 CH2)x ~N Ar NH2 (II) in which R2, Ar and x have the aforesaid meanings, to form an -NH-R3 group in which R is an acyl, sulfate or hydrochloride group, and reacting the resulting blocked diamine with an acryloyl or methacryloyl halide.
The starting aromatic diamine may be obtained by reacting ethylene oxide with an N-alkyl aniline, nitrosating the resulting N-hydroxyethylated N-alkyl aniline, and reducing the resulting p-nitroso-N-hydroxy-ethylated N-alkyl aniline. The reaction of the blocked diamine with the acryloyl or methacryloyl halide is preferable carried out in anhydrous pyridine to 5C for 1 hour and at 25-30C for 10 hours, and the acrylate ester thus produced is recovered by crystallization.
The acrylate esters described in the parent application are noted for their suitable copolymerization reactivity ratios .: . . . . . . . . :................ .
: ,:: . ~ : -: . . . - .
~Ol~3g5 with common monomers. They can be prepared as mono- or bifunctional monomers at the same time and, consequently, used for preparation of linear polymers soluble in proper solvents and insoluble crosslinked polymers.
The present divisional application is directed to polymers containing structural units of the general formula:
I / R
-cH2-f-co-(o-cH2-cH2)x-l-Ar-N (III) Rl R2 R5 wherein Rl is hydrogen or a methyl group, R is an alkyl or hydroxyalkyl containing 1 to 6 carbon atoms, R4 and R5 are the same or different and represent hydrogen, an acyl, sulfate or hydrochloric group, an alkyl containing 1 to 4 carbon atoms or a -CH2COOH group,with the proviso that R can represent an acyl, sulfate or hydrochloric group only when R4 is hydrogen, or R4 and R5 together with the nitrogen atom to which they are attached form a diazo group, Ar is p-phenylene, and x is 1 to 4.
Polymers of the above formula (III) in which R is hydrogen and ~5 is an acyl, sulfate or hydrochloric group, are prepared by a free-radical polymerization of the corresponding monomer of the formula~ (I) in the presence of an initiator of free-radical polymerization at or above the decomposition temperature of the initiator.
According to a preferred embodiment, the polymerization is carried out in the presence of comonomers consisting of monomers of the acrylic or methacrylic series, such as acrylamide, methacrylamide, acrylic acid, methacrylic acid and their esters, or of vinyl compounds, such as butadiene, isoprene and styrene.
- .
.
The polymerization is advantageously carried out in the presence of polymer solvents and precipitants or in a dispersion medium under formation of porous polymer particles having large inner surface area.
The invention enables to prepare a polymeric system, the chemical reactivity of which given by the conjugated nitrogen system allows to perform several reactions leading to products with specific properties. With respect to advantageous copolymerization reactivity ratios, especially with acrylates and methacrylates, materials of the defined structure with high content of reactive groups may be prepared. The copolymers may be indeed prepared also with other types of monomers, as with styrene, divinylbenzene and their derivatives, isoprene, butadiene, and the like.
The character of the reactive system prefers namely copolymerizations with monomers of hydrophilic nature, e.g. with esters containing hydroxyl group in the side chain, i.e. esters j of glycols, polyglycols or glycerol, with amides, i.e. acrylamide, methacrylamide, or N-substituted acrylamides and methacrylamides, and naturally, with methacrylic and acrylic acids.
The preparation of copolymers in the form of a three-dimensional network by copolymerization with multifunctional monomers, as for instance with divinylbenzene, ethylene glycol dimethacrylate or methylenebisacrylamide, leads to insoluble homogeneous or heterogeneous copolymers. In the presence of a suitable solvent system, polymers with large inner surface area and porosity are formed, which properties predetermine these ma-terials for broad application, namely those prepared in the form of small spherical particles for chromatographic and catalytic purposes and for ion exchange.
Polymers performed in this way may be transformed by further chemical conversions into materials useful for biological and technical applications.
Thus, polymers of the formula (III) in which R4 and R5 are hydrogen, alkyl containing 1 to 4 carbon atoms or -CH2COOI~
group, or R4 and R5 together with the nitrogen atom to they are attached form a diazo group, can be prepared by subjecting a preformed polymer of the formula (III) in which R4 is hydrogen and R5 is an acyl, sulfate or hydrochloric group to an acid hydrolysis and subjecting the resulting product to diazotization, alkylation or reaction with chloroacetic acid.
The reactive site is, for example, a primary aromatic amino group which may be diazotized and used in coupling reactions with various components.
Alkylation of the primary amino group may be carried out, for example, by reaction with formaldehyde (see Example 9) and leads to an aromatic tertiary alkylamine built into the polymeric skeleton.
The formation of a polymeric derivative of aminodiacetic acid is effected by reaction of the polymer with chloroacetic acid.
Polymers according to the invention may be advantageously used as ion exchangers, catalysts of chemical reactions and for biological applications.
The synthesis of monomers and polymers containing a p-phenylènediamine skeleton according to the inventions in the parent and divisional applications will now be further illustrated with reference to the following non-restrictive examples.
Example 1 N-Ethyl-N-(2-hydroxyethyl)-p-phenylenediamine (560 g) is dissolved in 2 1. of water at 45C, 230 g of acetanhydride is added under stirring and the mixture is neutralized with sodium hydroxide to the alkaline reaction (pH - 9). After dilution with three volumes of water, a crystalline product (m.p. 133C) is . . .... - . . . .
~ ,` 1081395 ; obtained, which is further reacted with methacryloyl chloride (10% excess) in the medium of anhydrous pyridine. Methacryloyl chloride is added into the reaction mixture at 5C within one hour and the temperature is then maintained at 25-30C under stirring for 10 hr. After dilution with 5 volumes of water, the oil separates which gives by crystallization from toluene and ethanol-water mixture the crystalline product (m.p. 93-94C).
Example 2 The monomer is prepared according to Example 1, with the distinction that acetate, sulfate or hydrochloride of N-ethyl-N-(2-hydroxyethyl)-p-phenylenediamine is used as the starting material and allowed to react with methacryloyl chloride according to Example 1.
Example 3 .
N-Ethylaniline (0.5 mole) is mixed with 0.6 mole of ethylene oxide in an autoclave, which is then sealed, pressurized with nitrogen to 30 atm and heated up to 130C within 2 hr.
Ethoxyethylated product is obtained in the yield of 95% related to the starting N-ethylaniline. This product is subjected to nitrosation at the temperature 5C with sodium nitrite solution, then reduced with tin in hydrochloric acid and, eventually, subjected to the methacrylation process according to Example 1.
Example 4 N-Ethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine (5 g) is dissolved in 10 g of Methylcellosolve and 0.01 g of azobisisobutyronitrile is added. The mixture is flushed with nitrogen and polymerized at 60C. The resulting polymer solution is diluted and precipitated into ether. The polymer is soluble inMethylcellosolve*,acetone and diluted hydrochloric acid.
* Trademark ~.' ' .
-` 1081395 Example 5 _ N-Ethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine (2.6 g) is mixed with 2.7 g of ethylene glycol monomethacrylate and 0.1 g of azobisisobutyronitrile.
Polymerization at 50 C gives a hard glossy material.
_xample 6 N-Ethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine (1 g) is dissolved in 4 g of methyl methacrylate and 1.3 wt. % of azobisisobutyronitrile is added. The mixture is sealed in an ampoule under nitrogen and gives after polymerization at 50C for 10 hours a glassy polymeric plug.
Example 7 N-Hydroxyethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine (1.5 g) is dissolved in 4.5 g of ethylene glycol monomethacrylate and 0.006 g (i.e., 0.1 wt. ~) of azo-bisisobutyronitrile is added. The mixture is transferred into a polymerization mold formed by two planparallel plates. The polymer resulting after polymerization at 60C for 8hrhas a form of a homogeneous plate.
_xample 8 A polymerization mixture consisting of 31.9 g of ethylene glycol dimethacrylate, 29.4 g of ethylene glycol mono-me-thacrylate, 20.4 g of N-ethyl-N-(2-methacryloyloxyethyl)-N'-acetyl-p-phenylenediamine and 0.82 g (1 wt. %) on monomers of azobisisobutyronitrile is polymérized with addition of 98.5 g of cyclohexanol and 9.7 g of dodecanol in a medium consisting of 600 g of watèr and 6 g of polyvinylpyrrolidone in a reactor at the temperature 50C for 2 hr and at 65C for further 8 hr.
Porous gel particles are obtained which exhibit the specific surface area 150 m2/g.
~081395 Example 9 The polymer prepared by the procedure described in Example 8 (5 g) was subjected to acid hydrolysis in diluted hydrochloric acid (l : l) by boiling for 30 min. This gel is mixed with 50 ml of 98% formic acid and 2 ml of 37% aqueous solution of formaldehyde is added under cooling. After 1 hr of stirring at the ambient temperature, the mixture is boiled (at 100 C) for 24 hr. The resulting gel - alkylated product - is washed with water and ethanol and dried.
Example 10 Diazotizing and coupling with 2-naphtol-3,6-sulfonic acid.
Diazotizing. The gel prepared by the procedure described in Example 8 and subjected to the acid hydrolysis described in Example 9 was washed and afterwards dispersed in hydrochloric acid 1 : 2. The suspension is cooled to -10C and a 10% solution of sodium nitrite is added under vigorous stirring within l hr in a 1.5 fold amount on NH2 groups of the polymer. After addition of the whole amount, the mixture is stirred at the same temperature for another 15 min. The gel is then filtered and thoroughly washed with water and five times with 0.5N HCl.
Coupling. An aqueous solution of 2-naphtol-3,6-sulfonic acid is poured into the filtered gel at 5C; -the resulting mixture has pH 1.5 - 2. The mixture is alkalized with borax under stirring;
coupling takes place at pH 7 , 8 which exhibits itself by turning the gel black the mixture is stirred for another 5 hr. On completion of the reaction, the gel is thoroughly washed with water, lN KOH, water lN H2SO4, water, and ethanol alternatively as long as the washing liquid is no longer colored.
The product is dried from ethanol and characterized by the amount of SO3H groups in the polymer.
` 1081395 _xample 11 Reaction with chloroacetic acid The gel after acid hydrolysis which was washed until the washing water was neutral is dispersed in a solution of sodium chloroacetate and sodium carbonate (1 mole of chloro-acetate and 0.5 mole of carbonate, the solution saturated at 70C). Twenty fold excess of chloroacetate on amount of NH2 groups is used. The mixture is stirred in an inert atmosphere at 95C for 8 hr. After cooling, the gel is filtered and thoroughly washed with lN HCl and water and dried from ethanol.
The product is characterized by the presence of functional groups / CH2-COOH in the polymer.
-N
g ~:
:
_ ........... . - ~ .
- : , . : ' . ,
Claims (12)
1. A polymer containing structural units of the general formula:
(III) wherein R1 is hydrogen or a methyl group, R2 is an alkyl or hydroxyalkyl containing 1 to 6 carbon atoms, R4 and R5 are the same or different and represent hydrogen, an acyl, sulfate or hydrochloric group, an alkyl containing 1, to 4 carbon atoms or a -CH2COOH group, with the proviso that R5 can represent an acyl, sulfate or hydrochloric group only when R4 is hydrogen, or R4 and R5 together with the nitrogen atom to which they are attached form a diazo group, Ar is p-phenylene, and x is 1 to 4.
(III) wherein R1 is hydrogen or a methyl group, R2 is an alkyl or hydroxyalkyl containing 1 to 6 carbon atoms, R4 and R5 are the same or different and represent hydrogen, an acyl, sulfate or hydrochloric group, an alkyl containing 1, to 4 carbon atoms or a -CH2COOH group, with the proviso that R5 can represent an acyl, sulfate or hydrochloric group only when R4 is hydrogen, or R4 and R5 together with the nitrogen atom to which they are attached form a diazo group, Ar is p-phenylene, and x is 1 to 4.
2. A polymer according to claim 1, wherein R4 is hydrogen and R5 is an acyl, sulfate or hydrochloric group.
3. A polymer according to claim 1, wherein R4 and R5 are hydrogen, alkyl containing from 1 to 4 carbon atoms or -CH2COOH group, or R4 and R5 together with the nitrogen atom to which they are attached form a diazo group.
4. A polymer according to claims 2 or 3, wherein R2 is an ethyl group.
5. A polymer according to claims 2 or 3, wherein x is 1.
6. A method of preparing a polymer according to claim 1, wherein an acrylate ester of the formula:
wherein R1 is hydrogen or a methyl group, R2 is an alkyl or hydroxyalkyl containing 1 to 6 carbon atoms, R3 is an acyl, sulfate or hydrochloric group, Ar is p-phenylene, and x is 1 to 4, is subjected to a free-radical polymerization in the presence of an initiator of free-radical polymerization at or above the decomposition temperature of the initiator to form a polymer containing structural units of the formula (III) defined in claim 1, in which R1, R2, Ar and x have the aforesaid meanings, R4.is hydrogen and R5 is an acyl, sulfate or hydro-chloric group, which, when required, is further subjected to an acid hydrolysis and the resulting product is diazotized, alkylated or reacted with chloroacetic acid.
wherein R1 is hydrogen or a methyl group, R2 is an alkyl or hydroxyalkyl containing 1 to 6 carbon atoms, R3 is an acyl, sulfate or hydrochloric group, Ar is p-phenylene, and x is 1 to 4, is subjected to a free-radical polymerization in the presence of an initiator of free-radical polymerization at or above the decomposition temperature of the initiator to form a polymer containing structural units of the formula (III) defined in claim 1, in which R1, R2, Ar and x have the aforesaid meanings, R4.is hydrogen and R5 is an acyl, sulfate or hydro-chloric group, which, when required, is further subjected to an acid hydrolysis and the resulting product is diazotized, alkylated or reacted with chloroacetic acid.
7. A method according to claim 6, wherein the polymerization is carried out in the presence of comonomers selected from the group consisting of acrylamide, methacrylamide, acrylic acid, methacrylic acid and the esters thereof.
8. A method according to claim 6, wherein the polymerization is carried out in the presence of comonomers selected from the group consisting of butadiene, isoprene and styrene.
9. A method according to claim 6, wherein the polymerization is carried out in the presence of comonomers selected from the group consisting of divinylbenzene, methylene-bisacrylamide and ethylene glycol dimethacrylate.
10. A method according to claim 6, wherein the polymerization is carried out in the presence of polymer solvents and precipitants.
11. A method according to claim 6, wherein the polymerization is carried out in a dispersion medium under formation of porous polymer particles having large inner surface area.
12. A method according to claim 6, wherein alkylation of the primary amino group is carried by reaction with formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA329,601A CA1081395A (en) | 1975-12-04 | 1979-06-12 | Polymers containing a reactive aromatic system and method for their preparation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA241,036A CA1071230A (en) | 1975-12-04 | 1975-12-04 | Monomers containing a reactive aromatic system and method for their preparation |
| CA329,601A CA1081395A (en) | 1975-12-04 | 1979-06-12 | Polymers containing a reactive aromatic system and method for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1081395A true CA1081395A (en) | 1980-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA329,601A Expired CA1081395A (en) | 1975-12-04 | 1979-06-12 | Polymers containing a reactive aromatic system and method for their preparation |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1081395A (en) |
-
1979
- 1979-06-12 CA CA329,601A patent/CA1081395A/en not_active Expired
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