JPS6183207A - Production of vinylimidazoline polymer - Google Patents

Abstract

PURPOSE:To obtain a high-quality vinylimidazoline polymer in good workability, by dispersing a nitrile-containing polymer and an alkylenepolyamine in a hydrocarbon solvent with the aid of a carboxylated hydrocarbon wax and reacting them. CONSTITUTION:A nitrile-containing polymer such as polyacrylonitrile or an acrylonitrile/ethyl acrylate copolymer and an alkylenepolyamine (e.g., ethylenediamine) are dispersed in a hydrocarbon solvent such as n-hexane or toluene with the aid of a carboxylated hydrocarbon wax and reacted with each other. In this way, a vinylimidazoline polymer useful as a polymer coagulant for waste water treatment can be produced without formation of lumps or the like. Examples of the carboxylated hydrocarbon was include oxidation product obtained by oxidizing petroleum wax such as paraffin wax and hydrocarbon wax such as low-MW polyethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing vinylimidazoline polymers.

[Conventional technology]

Vinylimidazoline polymers have long been known as polymer flocculants for wastewater treatment. Conventionally, as a method for producing polyvinylimidazoline polymers, a method is known in which a nitrile-containing polymer is reacted with ethylenediamine in a non-solvent such as hexane or heptane without a dispersant or in a state in which it is dispersed with a colloidal silicate. (For example,
However, in this method, the reaction product becomes lumpy during the reaction and cannot be taken out from a normal reaction tank, and the reaction tends to be extremely non-uniform, resulting in only low-quality products being obtained.

[Problem that the invention seeks to solve]

In view of the current situation, the present inventors investigated a method for industrially producing a high-quality vinylimidazoline polymer with good workability, and arrived at the present invention.

[Means to solve the problem]

The present invention provides a method for producing a vinylimidazoline polymer by reacting a nitrile-containing polymer and an alkylene polyamine, using a hydrocarbon wax obtained by carboxylating a nitrile-containing polymer and an alkylene polyamine in a hydrocarbon solvent. This is a method for producing polyvinylimidazoline polymers whose special feature is dispersion and reaction.

Examples of the carboxylated hydrocarbon wax in the present invention include oxidation products obtained by oxidizing hydrocarbon waxes such as petroleum waxes and polyolefin waxes.

In the above, paraffin wax (
For example, the number of carbon atoms is usually 20 or more, especially 26 to 30, and the melting point is 3.
7-65°C) Microcrystalline wax (carbon number usually 30-70
), petrolatum (melting point usually 38-6°C).

Examples of polyolefin waxes include low molecular weight polyethylene, low molecular weight polypropylene, and low molecular weight ethylene-olefin (usually having 3 to 8 carbon atoms) copolymers (for example, 50% or more ethylene, especially 70% or more). It will be done.

The average molecular weight of the above polyolefin wax is usually 500.
~10000, preferably 800~5ooo
It is.

The above polyolefin wax is a high molecular weight polyolefin (molecular weight usually 10,000 to 2,000,000) that is thermally degraded (pyrolyzed).
or by single or well polymerization of olefins. In some cases, it is also possible to use a low molecular weight polyolefin that is produced as a by-product during the production of high molecular weight polyolefins. There are two or more types of hydrocarbon waxes.
- (eg polyethylene wax and paraffin wax) may be used in combination.

To oxidize hydrocarbon wax such as petroleum wax and polyolefin wax, hydrocarbon wax is oxidized in a molten state or at a temperature below the melting point and above 90°C with water or an organic dispersion medium (hydrocarbon oil, halogenated hydrocarbon, etc.). Examples include a method of oxidizing with oxygen or an oxygen-containing gas (air) in a state dispersed in the air, and a method of oxidizing with ozone-containing oxygen or an ozone-containing gas (air). However, in the case of oxidizing polyolefin wax obtained by thermal degradation, it can be oxidized by hydrogenation or oxidized with ozone-containing oxygen or ozone-containing air, and a product with good thermal stability can be obtained. Organic peroxide (ASnzoyl peroxide, etc.) during oxidation
A catalyst such as can also be present. It is also possible to oxidize a high molecular weight polyolefin at the same time as thermal degradation.

The acid value of the hydrocarbon Fuchs oxidation product obtained by the above oxidation method is usually 3 to 100, preferably 15 to 5.
It is 0. The softening point is usually 40-85°C for petroleum wax oxidation products, preferably 50-75°C, and 80-14 for polyolefin wax oxidation products.
0°C, preferably 90 to 120°C. In addition, the average molecular weight is usually 30 in the case of oxidation products of petroleum waxes.
0 or more, preferably 350 to 1,000, and in the case of polyolefin oxidation products, it is usually 500 to 10,000, preferably 800 to 5,000.

Preferred among these are oxidation products obtained by oxidizing low molecular weight polyethylene.

Examples of the nitrile-containing polymer in the present invention include (b) polymers of (meth)acrylonitrile monomer 5 (1-100 mol%) and 0-50 mol% of other ethylenically unsaturated monomers.

Other ethylenically unsaturated monomers include oil-soluble monomers such as aliphatic hydrocarbon vinyl monomers (olefinic hydrocarbons having 1 to 6 carbon atoms such as ethylene, propylene,
(1-butene, etc.), aromatic hydrocarbon vinyl monomers (styrene, α-alkylstyrene, etc.), halogen-containing vinyl monomers (vinyl chloride, vinylidene chloride, etc.), (meth)acrylate vinyl monomers derived from alcohols polymers [(meth)acrylates from monohydric alcohols having 1 to 20 carbon atoms, such as methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.], and Vinyl ester monomers (vinyl acetate, etc.), water-soluble monomers such as amide group-containing monomers [(meth)acrylamide vinyl lactam having 5 to 9 carbon atoms, such as N-vinylpyrrolidone, etc.], hydroxyl group-containing monomers monoethylenically unsaturated esters of polyols [such as hydroxyethyl (meth)acrylate, triethylene glycol (meth)acrylate, etc.], carboxyl group-containing monomers [(meth)acrylic acid, maleic acid, etc.], amino group-containing monomers [such as (meth)acrylic acid, maleic acid, etc.], polymers [amino group-containing esters of monoethylenically unsaturated mono- or dicarboxylic acids such as dimethylaminoethyl (meth)acrylate, dimethylaminoethyl fumarate, amino group-containing heterocyclic vinyl compounds such as N-vinylpyridine], o and Sulfonic acid (2)
Examples include group-containing monomers [3-(meth)acryloyloxypropanesulfonic acid (2), 2-(meth)acrylic□amido-2-methylpropanesulfonic acid@), vinylsulfonic acid (2)], and the like.

The average molecular weight of the nitrile-containing polymer can vary depending on the type of nitrile-containing polymer, but is usually 50.0.
00 to 6,000,000, preferably 200,
The range is from 000 to 2,000,000.

It is desirable that the particle size of the nitrile-containing polymer be adjusted in advance to usually be 1000μ or less, preferably 1007z or less, before being subjected to the reaction. If the particle size exceeds 1000μ, the dispersion state of the reaction system becomes unstable and the reaction tends to become non-uniform.The particle size may be adjusted using a fine powder frame of a solid nitrile-containing polymer, or it may be mixed in an aqueous medium. Monomers may be emulsified or suspended (co)polymerized to obtain particles with a predetermined particle size.

Examples of alkylene polyamines include alkylene diamines having 2 to 8 carbon atoms, such as ethylenediamine, 1,2-diaminopropane, 1,2-diaminobutane, 1,2-diaminohexane, 1,3-diaminopropane, and 3-diaminobutane. , 1, δ-diaminohexane, 2,3-diaminopentane, 3,4-diaminohexane, 1,2-
Diaminocyclohexane, N-methylmethylenediamine, N-benzylethylenediamine, N-methyl-1,3
-diaminopropane, N-butyl-1,3-diaminopropane, N1N-dimethyl-1,3-diaminopropane, and mixtures of two or more thereof.

The hydrocarbon solvent used in the present invention is not particularly limited as long as it is a non-solvent for both the nitrile-containing polymer and the product vinylimidazoline polymer, but typical examples include aliphatic solvents. Hydrocarbons [n-hexane, n-hebutane, n-octane, n-decane, etc.], aromatic hydrocarbons (o-j F” or p-xylene, toluene, naphthalene, anthracene, etc.), alicyclic Hydrocarbons (cyclohexane, methylcyclohexane, cyclododecane, etc.), commercially available hydrocarbon mixtures (mineral spirits, gasoline, kerosene, light oil, terpenes, naphthenic solvent naphtha, octane fractions including mixtures of octane isomers, etc.) ) and mineral oil ivy
Examples include bottle oil, spindle oil, liquid paraffin, and white kerosene. Preferred among these are aliphatic hydrocarbons and mineral oil.

In the present invention, the amount of alkylene polyamine may be chemically equivalent to the nitrile component of the nitrile-containing polymer, but in this case the reaction tends to be incomplete. Therefore, the amount of alkylene polyamine is usually 1 mole of nitrile group.
．． The amount is 2 to 100 mol, preferably 2.0 to 5.0 mol.

The amount of carboxylated hydrocarbon wax is usually from 1 to 200%, preferably from 5 to 100%, based on the weight of the nitrile polymer. If the amount of carboxylated hydrocarbon wax is less than 1%, it will be difficult to maintain a dispersed state of the reaction system, and if it exceeds 200%, it will be disadvantageous in terms of cost.

The amount of hydrocarbon solvent is usually in the range of 0.5 to 20 times, preferably in the range of 2 to 10 times, based on the weight of the nitrile-containing polymer. Outside this range, the dispersion of the nitrile-containing polymer and vinylimidazoline polymer may become unstable and the reaction may become non-uniform.

When reacting a nitrile-containing polymer and an alkylene polyamine, reaction conditions are not particularly limited, but the nitrile-containing polymer and alkylene polyamine are usually dispersed in a hydrocarbon solvent using the carboxylated hydrocarbon wax of the present invention. Let me do it.

The reaction is accelerated by the use of catalysts. Suitable catalysts are sulfur or molecules comprising compounds containing thiol groups and at least one sulfur atom which forms a thiol group under the reaction conditions. Typical examples include alkali metal sulfides (e.g. sodium or potassium sulfide and other metal sulfides) thiobenzoic acid, thioacetic acid, thiopropionic acid, thioacetamide, thiobenzanilide, thioglycolic acid, hydrogen sulfide, ammonium sulfide, para Examples include toluenesulfonic acid. Preferably it is sulfur.

The reaction temperature is usually 65°C to 130°C, preferably 75°C.
°C to 110 °C. The reaction time is usually 1 to 10 hours, preferably 4 to 10 hours.

The reaction is completed and a stable suspension of vinylimidazoline polymer is obtained. This can be taken out in powder form and used by simple operations such as filtration. Further, if necessary, salts of general inorganic acids (hydrochloric acid, sulfuric acid, etc.) and organic acids (formic acid, acetic acid, etc.) may be used. Furthermore, if necessary during filtration, the powder may be washed with a small amount of a solvent such as acetone or ether, or the powder after filtration may be dried under reduced pressure or normal pressure.

The cationic degree and intrinsic viscosity of the vinylimidazoline polymer obtained in the present invention are not particularly limited and may be arbitrary, but from the viewpoint of usefulness as a polymer flocculant, those having a high cationic degree and intrinsic viscosity are preferable.

The degree of cation is usually 8.0 meq/g or more, preferably 4.0 meqy in terms of colloid equivalent value (measured at PH = 4).
! 7 or more, and the intrinsic viscosity (in 0.1N NaCl,
(measured at 80'C) is usually 20 or more, preferably 30 or more.
Two.

〔Example〕

The present invention will be further explained below with reference to Examples and Comparative Examples, but these are not intended to limit the present invention.

Example 1 80 g of n-hebutane 1 carboxylated hydrocarbon wax (
b) (Acid value 20, softening point 110°C1 average molecular weight 150
0) 6.4 g, polyacrylonitrile (particle size 100
7/ 21.2 g (molecular weight: approximately 900,000) and 84 da of ethylenediamine were added under stirring and uniformly dispersed.

Separately, a solution of 0.4 g of sulfur dissolved in 12 g of ethylenediamine was added little by little to the reaction system, and the reaction was carried out at 80° C. for 6 hours under a nitrogen stream. After that, excess ethylenediamine was recovered by vacuum distillation, and then cooled and heated to 196 g of sulfuric acid at room temperature.
The resulting suspension was filtered to obtain vinylimidazoline polymer 56, which is a pearl-like powder with a particle size of 500μ or less.
I got y. Upon filtration, the polymer had a uniform granular shape and no agglomerates were observed.

The recovered powder dissolves uniformly in water and has a colloid equivalent value of 5.9.
meq-/'-1i', intrinsic viscosity (0, IN N
aC1180°C) was 45.

Examples 2 to 4 The same conditions and operations as in Example 1 were carried out except for the conditions listed in Table 1. In both cases, after the reaction, there is no agglomeration and a stable suspension state with good flow during filtration (Note) 1. Carboxylated hydrocarbon wax (A): acid value 30, softening point 90°C, average molecular weight 200TV2, carboxylated hydrocarbon wax (B): acid value 20, softening point 110°C, average molecular weight 4. 500 things 8,
PAN polyacrylonitrile 4, intrinsic viscosity: d5
/g; 0. IN NaCl, 80'C5, colloidal equivalent value; meq, /da; PH4 Comparative Examples 1 to 3 The dispersant (carboxylated hydrocarbon wax) and solvent in the present invention of Example 1 were used under the conditions listed in Table 2. The experiment was carried out under the same conditions and with the same operation except that

In both cases, the polymer agglomerated during the reaction, and the polymer that could be taken out from the flask contained many water-insoluble materials and had an intrinsic viscosity of 10%.
It is a molar adduct.

〔Effect of the invention〕

According to the present invention, it is possible to produce a high-quality vinylimidazoline polymer with good workability.

In addition, in the production method of the present invention, the vinylimidazoline polymer has a high molecular weight that is extremely useful as a polymer flocculant, without problems such as the polymer main chain being broken during the reaction and only a low molecular weight polymer being obtained. It is easy to get things.

Furthermore, even as an industrial production method, it is very advantageous in terms of cost, as it does not require a reaction solvent or a precipitation solvent, and the reaction vessel used can be a very ordinary one.

Claims (1)

[Claims] 1. In a method for producing a vinylimidazoline polymer by reacting a nitrile-containing polymer and an alkylene polyamine, the nitrile-containing polymer and alkylene polyamine are dispersed in a hydrocarbon solvent using a carboxylated hydrocarbon wax. 1. A method for producing a vinylimidazoline polymer, which comprises reacting the vinylimidazoline polymer.