JPS59172510A - Basic linear copolymer and its production - Google Patents

Abstract

PURPOSE:To obtan a basic linear copolymer suitable for use in metal extraction, paint materials, etc., by copolymerizing a specified benzimidazole monomer with a vinyl monomer. CONSTITUTION:A monomer of formula I (wherein R1 is H or a 1-4C hydrocarbon, Z is a group of formula II or III, R2 and R3 are each H or a 1-10C hydrocarbon, and Y<-> is a counter ion), e.g., 2-(m-vinylphenyl)benzimidazole, with a monomer of formula IV (wherein A and B are each H, a 1-10C alkyl, haloalkyl, halogen, cyano, aryl, halogenophenyl, 1-5C alkylphenyl, haloalkylphenyl, or the like), e.g., styrene or acrylonitrile. In this way, the purpose linear copolymer comprising polymer units of formulas V and VI and having 10-90mol% polymer units of formula V and a MW of 1,000-2,000,000 is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel basic copolymer and a method for producing the same.

Polymers having basicity are used for various purposes by taking advantage of their basicity. Examples include corrupted materials, sizing materials, and metal oils. However, conventionally known basic polymers cannot necessarily be said to have excellent weather resistance and oxidation resistance. From this point of view, the inventors conducted various studies and as a result discovered the basic copolymer shown below.

That is, the novel copolymer according to the present invention has the following structural formula (
1) and ([consisting of polymerized units represented by 1, (11
Molecular weight 1000 containing 10 to 90 mol% of polymerized units of
It is a linear copolymer of 2.000.000 to 2.000.000.

(1) (II) However, R1 represents an aqueous group or a hydrocarbon group having 1 to 4 carbon atoms. A and B are hydrogen, alkyl group having 1 to 10 carbon atoms or haloalkyl, +, Q, halogen, cyan group, aryl group, halogenophenyl group, alkylphenyl group having 1 to 5 carbon atoms or haloalkylphenyl)b, 000R4(
R4 is hydrogen or carbon number 1 to lOO reverted hydrogen hydride group C
O 几5 (几5 is a hydrocarbon group having 1 to 10 carbon atoms), 00
0R6 (R, 6 is a hydrocarbon group having carbons a1 to 10), 0
ONHR? (R represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), an imidazole group, a pyridyl group, or a carbazole group.

Also, Z represents the following (a) or (b).

2 (a)
(b) Here, R2,)+3 represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and Y- represents a counter anion.

+1. Preferred examples include hydrogen, methyl group, and ethyl dihydrogen, among which water systems are preferred.

Preferred examples of R2 and R13 include hydrogen, methyl group, ethyl group, propyl group, dithyl group, and benzyl group.

Although R8 and Z in formula +11 may be placed in any position, Z is preferably at the meta or ξ position relative to the vinyl group, and R is also preferably at the meta or para position.

Y- represents a counter anion to the imidazolium cation in formula (b), and is not particularly limited as long as it can easily become an anion, even if it is a polyvalent anion such as a sulfate ion or a phosphate ion. good. Specific examples include nitrogen ions, hydroxy ions, carbonate ions, nitrate ions, sulfate ions, and phosphate ions.

The molar fraction of the polymerized units represented by formula (1) in the copolymer is 10 to 90 mol%, more preferably 20 to 90 mol%.
~80 mol%. The polymerized unit represented by formula (1) is not a single substance, and may contain two or more polymerized units having different R and/or 2.

On the other hand, the mol% of the weight ratio shown in formula (■) is 10 to 9
It is 0 mol%, preferably 20 to 80 mol%.

Preferred examples of A and H are hydrogen, cyan group, chloro group, methyl group, phenyl group and 0OOH.

OOOMe, 00Me, OOOMe, 0O
Such as NH2. There is nothing wrong with formula (II) also including a plurality of different N prefixes of A and H.

The molecule 1+1 of the copolymer in the present invention is 1000 to 2.000,000, more preferably 100
~2,000,000.

The copolymer of the present invention can be obtained by co-adding jtj to a half-mer represented by the structural formula (llll) and a harmonic body represented by the structural formula.

(2) (1.Z, A and B are the same as above. (p-vinylphenyl)penzimitazole, 2-(3-methyl-5-vinylphenyl)henzii1zole, 2-(3-ethyl-5-vinylphenyl)minzimidazole, 2-(3
-benzyl-5-0nylphenyl)penzimitasol, 1-methyl-2-(vinylphenyl)benzimidazolium chloride, l,3-dimethyl-2-(vinylphenyl)benzimidazolium chloride, l-methyl- 2
-(3-methyl-5-vinylphenyl)benzimidazolium chloride, l-methyl-2-(:i-ethyl-5
-vinylphenyl)benzimidazolium chloride, l
-Methyl-2-(3-benzyl-5-vinylphenyl)
Penzimidazolium chloride r, t, 3-, y methyl-
2-(Methyl-5-vinylphenyl)penzimidazolium chloride, 1,3-dimethyl-2-(3-ethyl-5τvinylphenyl)penzimitazolium chloride, 1-methyl-3-ethyl-2-( Examples include vinylphenyl)benzimidazolium bromide, l-methyl-3-benzyl-2-(hinylphenyl)penzimidazolium chloride, and the like.

Examples of monomers represented by the structural formula ■ include styrene, methylstyrene, diphenylethylene, ethylstyrene,
Hydrocarbon compounds such as dimethylstyrene, vinylnaphthalene, vinylphenanthrene, vinylmestyrene, 3.4.6-)dimethylstyrene; chlorstyrene, haxystyrene, bromustyrene, cyanostyrene, fluorostyrene, dichlorostyrene, chloro Styrene derivatives such as methylstyrene, trifluorostyrene, trifluoromethylstyrene; Acrylonitrile derivatives such as acrylonitrile, methacrylonitrile, α-acetoxyacrylonitrile; Acrylic acid, methacrylic acid; Methyl acrylate, lauryl acrylate, chloromethyl acrylate, acetoxy Acrylic acid esters such as ethyl acrylate; Methacrylic esters such as cyclohexyl methacrylate; Diethyl maleate, diethyl fumarate: Vinyl ketones such as methyl vinyl ketone and ethyl isozolobenyl ketone: Vinylidene chloride, vinylidene bromide, vinylidene cyanide Vinylidene compounds such as acrylamide, methacrylamide, N-phenylacrylamide, vinyl acetate, vinyl butyrate, vinyl caprate, fatty acid vinyl derivatives; and N-vinylcarbazole, vinylimidazole, methylvinylimidazole , vinylpyridine, methylvinylpyridine, and other heterocyclic vinyl compounds.

Among these, A and B are hydrogen, a cyano group, a chloro group, a methyl group, a phenyl group, and 0OOH and 000Me.

More preferred are 00Me, 000Me, and 0ONH1.

When producing the copolymer of the present invention using monomers represented by the structural formula [phase] and (■), there are no particular restrictions on the polymerization method, and polymerization by heating is sufficient, but polymerization using a polymerization initiator is sufficient. It is often preferable to do so. The polymerization initiators used include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, azobisisomethylnitrile, and
．． Azonitriles such as 2'-azobis(2,4-,)methylmaleronitrile), peroxides such as ditertiary methyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxyr, cumene hydroperoxide, tertiary
These are hydroperoxides such as hydroperoxide.

The polymer in the present invention can also be produced by polymerizing in the presence of an inert liquid. Inert liquids include aliphatic hydrocarbons such as normal pentane, normal hexane, normal heptane, and noryl-octane, alcohols such as methanol, ethanol, and isozorobyl alcohol, acetone, methyl ethyl ketone, Ketones such as diethyl ketone, diethyl ether, methyl ethyl ether, dibutyl ether, dioxane, ethers of tetrahydrofuran, aromatic hydrocarbons of benzene, toluene, xylene, esters such as diethyl ether, ethyl acetate, methyl acetate, etc. Amides such as dimethylformamide and dimethylacetamide; aliphatic halides such as chloroform, methylene chloride, and dichloroethane; aromatic halides such as chlorozene; and polar liquids such as dimethylsulfoxy P. Can be used. These liquids can be used alone or as a mixture of two or more liquids.

There is no limit to the temperature of the reaction, but it is preferably about 20°C to 120°C, more preferably about 60°C to ioo°C.

Furthermore, as a method for obtaining a copolymer corresponding to Z=(b) of the copolymer of the present invention, it can also be obtained by reacting a copolymer corresponding to z=(a) with R3X. (几3 is the same as above, but X is a halogen.) If Y=X, no further processing is required, but if Y=IIFX,
It is necessary to exchange ions from - to Y-.

The amounts of R and X are preferably equal to or more than the mole of the benzimidazole skeleton of the raw material, and more preferably 1 to 10 times the mole.

There is no particular restriction on the reaction temperature and time, but usually 20 to 10
The temperature is 0° C. for about 1 hour to 50 hours. The reaction may be carried out in the presence of an inert liquid.

Additionally, in this reaction, it may be advantageous to add a basic substance. Basic substances include alkali metal salts such as potassium hydroxide, sodium hydroxide, and sodium carbonate, and even alkaline alcoholades such as sodium ethylate.

There is no particular restriction on the amount of the basic substance used, but the '1 functional group (
It is preferably 0.1 to 10 times the mole of a), more preferably 1 to 3 times the mole.

When trying to obtain a copolymer in which 2 is (b) and R and R3 are equal, compound R2X (= 1RsX
) can also be obtained by reacting twice the molar amount.

When R or R3 is hydrogen, (■) can tautomically convert the amine series with an acid or a base.

It has been found that the copolymer of the present invention has a benzimidazole or benzimidazolium skeleton in the side chain, and can be used for metal extraction, paint materials, sizing materials, etc.

Examples of the present invention are shown below, but these are not intended to limit the present invention.

Example 50 - 11.0 gr of 2-(p-vinylphenyl)benzimidazole in an ampoule tube,! : , 5.2 g
r Nostyrene and 0.1 f azobisisozothyronitrile were mixed, and the inside of the ampoule tube was irradiated with nitrogen gas. After immersing this in a 90°C water bath for 18 hours, the seal was broken and the solidified contents were taken out. The main peaks in the elemental analysis and infrared absorption spectrum of this product are as follows.

Elemental analysis values: The values in parentheses represent theoretical values.

0; 85.05 (85,15) H; 6.22
(6,21)N; 8.73 (8,63) Infrared absorption spectrum; unit α-1 34G0, 3050, 1620, 1600, 1
490, 1450.

1280, 740, 700 and other solids were obtained, totaling 16.2 g (yield: 100
'A). The obtained solid O,S t is 100d
When mixed with 2N hydrochloric acid, all of this solid was dissolved, and not a single oily liquid was floating on the surface of the hydrochloric acid.

In the infrared absorption spectrum, the peak attributable to the double bond of 2-(p-
It was concluded that it was a copolymer of (vinylphenyl)benzimidazole and styrene.

When this product was subjected to molecular plate measurement using gel-nosedition chromatography using polystyrene as a calibration curve, it was found to be 1,200,000.

This copolymer 12 and ferric chloride (molecular formula Feels 6
H,0) 0.270 f was dissolved in 2N hydrochloric acid (Ip
f and the whole image was set to 50α. After extracting this solution Q50et five times with chloroporm, the iron concentration in the hydrochloric acid was measured and found to be 1 mmol/l.

On the other hand, when chloroform extraction was performed on a similar ferric chloride hydrochloric acid solution that did not contain this copolymer, the iron concentration was 19 mmol/l, and the concentration hardly changed before and after the extraction. These results indicate that this polymer can be used as an extractant for Kanahashi.

Implementation 1+12-15 Copolymerization of the monomer represented by the structural formula ([0) and the monomer represented by the structural formula (goods) was carried out using the same method as in Example 1 under the same conditions. . The results are summarized in Table IK.

Example 13.56 gr of the polymer obtained in Example 2 was mixed with methanol II! Sodium ethylate 2
．． 72 gr was added and stirred at 50°C. To this, 11.4 gr of methyl iodide was added dropwise over 30 minutes, and the reaction was continued for 5 hours. The reaction mixture was reprecipitated from ether and dried under reduced pressure to obtain the product.

When the amount of strong base in the product was measured, it was found to be 2.51me>/f(
Y=O1. This revealed that 100% of the benzimidazole skeleton was N-methylated to produce a 1,3-dimethylbenzimidazolium compound.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

Scope of Claims: (11) A linear copolymer of 1000 to 2,000,000 molecules jli consisting of polymerized units represented by the following structural formulas (1) and III and containing 10 to 90 mol% of the polymerized units. Polymer (I)
(River) However, R1 is hydrogen or has 1 to 4 carbon atoms.
represents a hydrocarbon group. A and B are hydrogen, an alkyl group or haloalkyl group having 1 to 10 carbon atoms, halogen,
4'Ti group, aryl! Run, halogenohue = le 4
, carbon@1-5 alkylphenyl group or haloalkylphenyl Q, 000R4 (R4 is hydrogen or carbon number 1
to lO hydrocarbon group), 00R5 (n, , is the number of carbon atoms l
to 10 hydrocarbon groups), 0CORs (Re is a hydrocarbon group having 1 to 10 carbon atoms), 0ONH(Ry is hydrogen or a linear hydrogen method having 1 to 10 carbon atoms), imidazole group, pyridyl group, or carbazole represents a group. Also 2
represents the following (a) or (b). 3 ■ (a)
(b) Here, R,, R, represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and Y- represents a counter anion. (2) A method characterized by polymerizing the monomers shown in the following expressions! (2) Molecules consisting of polymerized units represented by the following structural formulas (1) and (If) and containing 10 to 60 mol% of the polymerized units of (1)! Method for producing a linear copolymer with a molecular weight of 1,000 to 2,000,000 (1) (n) However, 几! represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. A and B are hydrogen, alkyl groups or haloalkyl groups from longitudinal cables a1 to IO, halogens, cyano groups, aryl groups, halogenophenyl groups, alkylphenyl groups having 1 to 5 carbon atoms, and haloalkylphenyl threads, 000Ra (几4 is Hydrogen or hydrocarbons having 1 to 10 carbon atoms, +J: ), CO
Rg (5 is the number of carbon atoms! to 10 hydrocarbons & l, 00
0Rs (1- is hydrocarbon number 71 with carbon number 1 to io)
, 0ONH 7 (R7 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), imidazole nor, pyridyl group or carbazole group. Also, Z represents the following (a) 1 mouth). ” ■− (a)
(b) Here, R2 and 几3 are hydrogen or carbon atoms 1 to 10
In the hydrocarbon group, Y- represents a counter anion. (3) Structural formulas (1) and (II) in which z has a structure with a symbol
Polymerization represented by the following structural formulas (1) and (II), which is characterized by reacting R and X with a copolymer consisting of polymerized units represented by unit, containing 10 to 90 mol% of the polymerized unit of (1) and having a molecular weight of 1,000 to 2,000.00
Method for producing a linear copolymer of 0 (I)
(■) (
b) However, R2 represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, R2 represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and X represents halogen. A and B are hydrogen, an alkyl group or haloalkyl group having 1 to 10 carbon atoms, a halogen, a cyano group, an aryl group, a halogenophenyl group, an alkylphenyl group having 1 to 5 carbon atoms or a haloalkylphenyl group, 0001'L4 (R4 is Hydrogen or carbon number I
to 10 hydrocarbon groups), CO 几5 (Rs is a hydrocarbon group having 1 to 10 carbon atoms 4i), 000 几5 (T- is a hydrocarbon group having 1 to 10 carbon atoms)
to 10 hydrocarbon group), 0ONI (R7 (Ry is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), imidazole group, pyridyl group, or carbazole group. Also, Z represents the following (b). 几3 ■ ■ L2 (b) Here, R3 represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. Y- represents a counter anion.