JPS6183205A - Production of vinylimidazoline polymer - Google Patents

Abstract

PURPOSE:To obtain a high-quality vinylmidazoline polymer in good workability, by dispersing a nitrile-containing polymer and an alkylenepolyamine in a hydrocarbon solvent with the aid of a specified copolymer and effecting a reaction. CONSTITUTION:A nitrile-containing polymer such as polyacrylo-nitrile 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 copolymer comprising an oil-soluble monomer except nitriles (e.g., propylene or styrene) and a water-soluble monomer (e.g., acrylamide or hydroxyethyl acrylate). This dispersion is allowed to react at a reaction temperature of about 65-130 deg.C for about 1-10 hr to obtain a vinylimidazoline polymer useful as a polymer coagulant for waste water treatment in good workability without formation of lumps.

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. A conventional method for producing polyvinylimidazoline polymers is to react a nitrile-containing polymer 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, special public relations
Publication No. 6271). However, in this method, the reaction product becomes lumpy during the reaction and cannot be removed 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, in which a nitrile-containing polymer and an alkylene polyamine are reacted with a non-nitrile oil-soluble monomer in a hydrocarbon solvent. This is a method for producing a vinyl-imidacyline polymer, which is characterized by dispersing and reacting a copolymer of a vinyl imidacyline and a water-soluble monomer.

The copolymer of the non-divine oil-soluble monomer and the water-soluble monomer in the present invention is not particularly limited, and any copolymer can be used.

Non-nitrile oil-soluble 11Njt bodies include aliphatic hydrocarbon yarn vinyl monomers (olefinic hydrocarbons having 1 to 6 carbon atoms, such as ethylene, propylene, 1-butene, etc.)
, aromatic hydrocarbon vinyl monomers (styrene, α-alkyl styrene, and vinyl monomers containing
(vinylene chloride, vinylitine chloride, etc.), (meth)acrylate-based vinyl monotons derived from alcohol [1 to 1 carbon atoms]
(meth)acrylates from monohydric alcohols such as methyl (meth)acrylate-1-, butyl (meth)acrylate-1-1-12-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.), and vinyl esters. System monomers (vinyl acetate, etc.) are produced. Among these, preferred are aliphatic hydrocarbon vinyl monomers, aromatic hydrocarbon vinyl monomers, and (meth)acrylate vinyl monomers derived from alcohols.

As water-soluble monomers, amide group-containing monomers “(meth)
acrylamide (vinyl lactams having 5 to 9 carbon atoms, such as N-vinylpyrrolidone), hydroxyl group-containing monomers (monoethylenically unsaturated esters of polyols, such as hydroxyethyl (meth)acrylate, triethylene glycol (meth)acrylate, etc.) , carboxyl group-containing monomer [(meth)acrylic acid,
maleic acid, etc.] amino group-containing monomer [monoethylene f
l Amino group-containing esters of saturated mono- or dicarboxylic acids, such as di,methylaminoethyl (meth)acrylate.

dimethylaminoethyl fumarate; amino group-containing heterocyclic vinyl compounds such as N-vinylpyridine], and sulfonic acid (salt) group-containing monomers [3-(meth)acryloyloxypropanesulfonic acid (salt), 2- (meth)acrylamido-2-methylpropaneforsonic acid (salt), vinylforsonic acid (salt), etc.). Among these, preferred are amide group-containing monomers, hydroxyl group-containing monomers and amine group-containing monomers.

The molar ratio of the oil-soluble monomer to the water-soluble monomer may be any ratio as long as the resulting copolymer is oil-soluble, or it is usually 40
．． /60 to 99/l, preferably 60/l
It ranges from 40 to 9515.

The molecular weight of the copolymer is usually io, ooo to 10,000.
,000, preferably from 100,000 to 5.0
The range is 00,000.

The copolymers of the present invention may contain small proportions of nitrile monomers (reportedly up to about 10 mol % in the copolymer).

Specific examples of the copolymer include a copolymer of lauryl methacrylate and N,N-dimethylaminoethyl methacrylate; a copolymer of butyl methacrylate 1note, 2-ethylhexyl methacrylate, and N-vinylpyrrolidone; a copolymer of styrene and Examples include a copolymer of methyl methacrylate 1 note and N,N-dimethylaminoethyl methacrylate; a copolymer of ethylene and acrylic acid; a copolymer of propylene and 71 note acid, and the like.

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

Other ethylenically unsaturated monomers include the oil-soluble monomers and water-soluble monomers described in the section on copolymers of non-nitrile oil-soluble monomers and water-soluble monomers.

Preferred among the nitrile-containing polymers are polyacrylonitrile, copolymers of acrylonitrile and ethyl acrylate, and copolymers of acrylonitrile and vinyl chloride.

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 5,000,000, preferably 200
,000 to 2,000,000. It is desirable that the particle size of the nitrile-containing polymer be adjusted in advance to usually be 1000 microns or less, preferably 100 microns or less, before being subjected to the reaction. When the particle size exceeds 1000 μm, the dispersion state of the reaction system becomes unstable and the reaction tends to be non-uniform.

The particle size may be adjusted by finely pulverizing a solid nitrile-containing polymer, or by emulsifying or suspending (co)polymerizing monomers in an aqueous medium to obtain a predetermined particle size. good.

The alkylene polyamine is an alkylene diamine having 2 to 8 carbon atoms, such as ethylene diamine.

1,2-diaminopropane, 1,2-diaminobutane.

1.2-diaminohexane, 1,3-diaminopropane, 1.3-diaminobutane, 1,3-diaminohexane, 2,8-diaminopentane, 3.4-diaminohexane, ■, 2-diaminocyclohexane, t[-methylmethylenediamine, N-benzylethylenediamine, N-
Methyl-1,3-diaminopropane.

N-butyl-1,3-diaminopropane and N,N-
Dimethyl-I, 3-diaminopropane and mixtures of two or more thereof are mentioned.

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 (nt
\Xylene n-heptane.

Aromatic hydrocarbons (o
-, m- or p-xylene, toluene.

naphthalene, anthracene, etc.), alicyclic hydrocarbons (
Cyclohexane, methylcyclohexane.

(cyclode Σ゛can, etc.), commercially available hydrocarbon mixtures (military spirit, gasoline, kerosene, etc.).

gas oils, thebenbenes, naphthenic solvent naphthas, octane fractions containing mixtures of ictane isomers, etc.) and mineral oils (turbine oils, spindle oils.

liquid paraffin, white kerosene, etc.).

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, alkylene polyamine nails are usually 1 mole of nitrile group.
2 to 100 mol, preferably 2.5 to 50 mol.

The amount of the copolymer of non-nitrile oil-soluble monomer and water-soluble monomer is usually 1 to 200%, preferably 2 to 80%, based on the weight of the nitrile polymer used. When the amount of copolymer is 1% US, it is difficult to maintain the dispersion state of the reaction system,
If it exceeds 0%, 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 1 () times, based on the weight of the nitrile-containing polymer. Outside this range, the dispersion of the nitrile-containing polymer and vinylimidazoline polymer is unstable and the reaction tends to be non-uniform.

When reacting a nitrile-containing polymer and an alkylene polyamine, reaction conditions are not particularly limited, but the reaction is usually carried out by dispersing the nitrile-containing polymer and alkylene polyamine in a hydrocarbon solvent using the copolymer of the present invention.

The reaction is accelerated by the use of catalysts. Suitable catalysts are sulfur or compounds containing thiol groups and molecules of at least 61 atoms of sulfur that form thiol groups under the reaction conditions. Typical examples are alkali metal sulfides (such as thorium or potassium sulfide and other metal sulfides), thiobenzoic acid, thioacetic acid, thiopropionic acid, thioacetamide, diobenzanilide, thioglycolic acid.

Examples include hydrogen sulfide, ammonium sulfide, and para-toluenesulfonic acid. Preferably it is sulfur.

The reaction temperature is usually 65°C to 130°C, preferably 75°C.
(: ~110°C. The reaction time is usually 1 to 10 hours, preferably ~16114 ffB. The reaction is completed and a stable suspension of the vinylimidazoline polymer is obtained. It can be taken out in powder form and used.If necessary, it may be converted into a salt of a general inorganic acid (hydrochloric acid, sulfuric acid, etc.) or an organic acid (formic acid, acetic acid, etc.). 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, it is preferable that the cationic degree and intrinsic viscosity are high.

The degree of cationicity is usually 8.0 meq/g or less in colloid market value (measured at pH = 4) - preferably 4.0 meqg/
g or more, and the intrinsic viscosity (0, I N NaC (! medium,
: Measured by JO'Q) is usually 2.0 or more, preferably 8
．． It is 0 or more.

〔Example〕

The present invention will be further explained below with reference to Examples and Comparative Examples.
However, this is not intended to limit the invention.

Example 1 In a 500 md four-flow flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a reflux condenser, 80 g of n-hebutane, 1 lauryl methacrylate, which is a copolymer of the present invention, and N
, N-dimethylaminoethyl methacrylate copolymer (
Molar ratio 90:10. 6.4 g of polyacrylonitrile (particle size: 100 μm or less, molecular weight: about 900,000), and 84 g 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 after cooling, 196 g of sulfuric acid was added at room temperature, and the resulting suspension was filtered to obtain 56 g of vinyl imidazoline polymer, which is a pearl-like powder with a particle size of 500 μm or less. Obtained. The filtered H-sound bundle showed a uniform granular shape, and no lumps were observed.

The recovered powder dissolves uniformly in water and has a colloid equivalent value of 6.0.
meq@/g *Intrinsic viscosity (0, IN NaC1,
80°C) was 4.4.

Examples 2-7 The conditions are the same as in Example 1 except for the conditions listed in Table-1.

The same procedure was used. Both become lumps after reaction (Note)
Intrinsic viscosity 2d, g/g; 0. I N NaCC80
°C colloid equivalent value: meq/g; pH42E
HMA: 2-ethylhexyl methacrylate, BM-A nibutyl methacrylate, VPY: N-vinylpyrrolidone, LMA nilauryl methacrylate, HEMA: pidroxyethyl methacrylate, MA: methacrylic acid, ST: Styl 1.・N, MMA: Methyl methacrylate, AEMA: N,N-dimethylaminoethyl methacrylate, SMA: Stearyl methacrylate-1, VP: Vinylpyridine, PAN: Polyacrylonitrile, N: Acrylonitrile, EA: Ethyl acrylate, → 10 wo → −F-rule ÷ 10 y → T VC = vinyl chloride, Comparative Examples 1 to 5 Table 2 shows the copolymer and solvent in the present invention of Example 1
The experiment was carried out under the same conditions and with the same operation except that the conditions (dispersant, solvent) were changed as described in .

In both cases, the polymer agglomerates during the reaction, and the polymer that can be removed from the flask contains many water-insoluble substances and has a limiting viscosity.

It was also impossible to measure the colloid equivalent value.

Table 2 (Note) The nonionic surfactant is a 10 mol adduct of nonylphenol ethylene oxide.

〔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, as an industrial production method, A7 is significantly superior in terms of cost, since no reaction solvent or precipitation solvent is required, and a conventional reaction tank may be used.

Claims (1)

[Claims] 1. A method for producing a vinylimidazoline polymer by reacting a nitrile-containing polymer and an alkylene polyamine, in which a nitrile-containing polymer and an alkylene polyamine are mixed in a hydrocarbon solvent, and a non-nitrile oil is reacted with the alkylene polyamine. A method for producing a vinylimidazoline polymer, which comprises dispersing and reacting a copolymer of a soluble monomer and a water-soluble monomer. 2. Claim 1, wherein the nitrile-containing polymer is a (co)polymer of 50-100 mol% of (meth)acrylonitrile monomer and 0-50 mol% of other ethylenically unsaturated monomers. Manufacturing method described in section.