JPS59184212A - Functional polymer and its production - Google Patents

Abstract

PURPOSE:To produce a functional polymer having flame retardancy and useful as a metal scavenger, by polymerizing a styrene derivative containing a 1,2- dihalogenoethyl group. CONSTITUTION:Divinylbenzene or its derivatives is reacted with a halogenating agent comprising deactivated halogen molecules to obtain a 1,2-dihalogenoethyl group-containing styrene derivative of formula I (wherein R is H, a 1-10C alkyl, aryl or aralkyl, and X1 and X2 are each a halogen). This styrene derivative is polymerized at 20-120 deg.C in an inert liquid (e.g., n-pentane) in the presence of a polymerization initiator (e.g., azobisisobutyronitrile) to obtain a linear high-MW (MW 1,000-2,000,000) polymer comprising polymer units of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel functional linear polymer and a method for producing the same, and more particularly, a polymer of a styrene derivative having a 1,2-dihalogenoethyl group and a method for producing the same. It is related to.

Many styrene derivatives have been developed and synthesized, and are widely used in the synthesis of functional polymers. For example, cyanostyrene, aminostyrene, etc. are easily polymerized by radical polymerization to provide polymers having various glaze functional groups.

As a 2-tyrene derivative with Rogge/atom,
Chlorostyrene, bromostyrene, chloromethylstyrene, no? 2-bromoethyl styrene and the like are known. Although many polymers of these compounds are known, no polymers of styrene derivatives having 1,2-dihalogenoethyl groups have been known so far.

The present inventor conducted various studies on functional polymer compounds having a halogenated alkyl group in the side chain, and as a result, discovered the novel functional polymer shown below.

That is, the present invention relates to a linear polymer consisting of polymerized units represented by the following structural formula (1) and having a molecular weight of 1,000 to 2,000,000.

CH2-x2 (wherein R represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, x, x2...
Represents Rogen. ) In structural formula (1), a preferred embodiment of X, X2 is the same or different combination of chlorine, bromine and iodine. Further, the preferable positional relationship between the main chain and the 1,2-dino-lognoethyl group is the meta position, the para position, or a mixture thereof.

The molecular weight of the linear polymer in the present invention is 1000 to 2
,000,000, more preferably from 10,000 to 2,000,000.

The linear polymer of the present invention can be obtained by polymerizing monomers represented by structural formula (II).

CH2=CH CH2-X2 (wherein R represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aracyl group, and XI.

X2 represents halogen. ) The above monomer can be obtained, for example, by reacting divinylbenzene or a substituted product thereof with a halogenating agent that has inactivated halogen molecules.

There are no particular restrictions on the polymerization method, and polymerization by heating is sufficient, but it is often preferable to use a polymerization initiator. The polymerization initiators used include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, azobisin butyronitrile, and 2,2'-azobis(2,4
-dimethylmaleronitrile), peroxides such as ditertiary butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, and hydroperoxides such as cumene hydroperoxide and tertiary hydroperoxide.

The polymer in the present invention can also be produced by polymerizing in the presence of an inert liquid. Examples of inert liquids include aliphatic hydrocarbons such as normal pentane, normal hexane, normal hebutane, and normal octane, alcohols such as methanol, ethanol, and isopropyl alcohol, acetone, methyl ethyl ketone, and diethyl ketone. ketones, ethers such as diethyl ether, methyl ethyl ether, dibutyl ether, dioxane, tetrahydrofuran, benzene,
Aromatic hydrocarbons such as toluene and xylene; esters such as ethyl formate, ethyl acetate and butyl acetate; amides such as dimethylformamide and dimethylacetamide; aliphatic halides such as chloroform, methylene chloride and dichloroethane; Aromatic halides such as chlorobenzene and polar liquids such as dimethyl sulfoxide can also be used. Note that these liquids can be used alone or as a mixture of two or more liquids.

There is no limit to the reaction temperature, but it is preferably about 20°C to 120°C, more preferably about 60°C to 100°C.

The copolymer of the present invention has an alkyl-substituted phenyl group having one halogen on each adjacent carbon, that is, a 1,2-dihalogenoethyl phenyl group in the side chain, and can be converted into various functional groups by various reactions. Therefore, it is useful as a functional polymer.

For example, by reaction with a nitrogen compound, it is possible to produce a polymer having anion exchange or a polymer having the ability to chelate various imino-metals.

Similarly to this case, similar polymers can be synthesized using alkyl-substituted styrenes having one halogen atom, such as ξ-(2-bromoethyl)styrene and chloromethylstyrene copolymers. However, there are very large qualitative differences in the performance of the synthesized polymers. For example, the difference is obvious in chelate polymers into which iminodiacetic acid groups have been introduced.

When iminodiacetic acid groups are introduced into a polymer produced from 1.2-dihalogenoethylstyrene, a side chain in which two iminodiacetic acid groups are arranged is produced. It is represented by the structural formula @) below.

On the other hand, when an iminodiacetic acid group is introduced into a polymer produced from chloromethylstyrene, for example, the following structural formula is obtained.

Here, if we compare the structural formula @) and the side chain of (goods), the rule)
It can be seen that the chelate polymer synthesized from the polymer of the present invention is very effective as a metal removing agent.

Furthermore, the polymer of the present invention is useful as a flame-retardant polymer because it has two nitrogen atoms in the side chain.

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

In an ampoule of Example 50, 5.0 P of 3-(1,2-dibromoethyl)styrene, 20 fnl of xylene and 0.0
After adding 551-azobisinobutyronitrile and thoroughly mixing and dissolving the ampoule, the inside of the ampoule was purged with air and the tube was sealed. This was immersed in a 90°C water bath for 24 hours. After cooling, the sealed tube was broken, the contents were poured into hexane, the precipitate was filtered out, and the precipitate was optically washed with hexane, dried under vacuum, and the weight was measured and found to be 4.9ψ. The elemental analysis values and main peaks in the infrared absorption spectrum of this product are as follows.

Elemental analysis value (the value in parentheses represents the theoretical value) C; 41.3
8(41,42)H;3.42(3,48)Br;55
．． 20(55,11) Infrared absorption spectrum (c1n') 3020.2970, 1600, 1510, 1480,
1215°8od, 690 It was confirmed that it was a polymer because the absorption derived from the C═C double bond in the monomer disappeared.

The molecular weight of this product was determined by gel ξ-meation chromatography using polystyrene as a calibration curve, and the molecular weight was 1.1o.
It was o, o o o.

Example 2 The reaction and operation were carried out in exactly the same manner as in Example 1, except that 4-(1,2-dibromoethyl)styrene was used as a substitute for 3(i+2)bromoethyl)styrene. The yield of the obtained product was 4.8z, and its elemental analysis values and main peaks in the infrared absorption spectrum are as follows.

Elemental analysis value (the value in brackets represents the theoretical value) C: 41.3
5(41,42)H:3.39(3,48)Br;5
5.26(55,11) Infrared absorption spectrum (crn-') 3020.2910,1600,1510,1430°1230.835,695 When the molecular weight was measured in the same manner as in Example 1, the molecular weight was 900, It was 000.

Example 3 10. After adding OF's 3-(1,2-dibromoethyl)styrene, 20ml (D propatool) and 0051's asobisin butyronitrile and thoroughly mixing and dissolving them, the inside of the ampoule tube was diluted with nitrogen and sealed. This was immersed in a 90°C water bath for 24 hours. After cooling, the sealed tube was broken and the contents were placed in a 4-day flask equipped with a thermometer, reflux, and stirrer. 100 mA of ethanol in which 26.19 - of acetic acid ethyl ester was dissolved was added, and stirring was continued for 24 hours while keeping the internal temperature at 70 °C. Next, 100 mA of pure water in which 6.61 - of sodium hydroxide was dissolved was added, and the mixture was heated to 90 °C. Stirring was continued for an additional 5 hours.After cooling and washing, metal removal ability was examined as shown in the figure.

Dissolving divalent Cu chloride and trivalent Fe chloride in pure water,
Water-soluble giz containing 1001n9 of each metal was prepared.

Add the polymer synthesized as described above to this aqueous solution 5. Oz
was added and immersed for 24 hours, and the amount of metal ions remaining in the aqueous solution was measured, and both Cu and Fe were 0.11n9 or less.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Scope of Claims] 1 A linear polymer having a molecular weight of 1,000 to 2,000,000 composed of polymerized units represented by the following structural formula (1) (wherein R is hydrogen and has a carbon number of 1 to 10 represents an alkyl group, aryl group or aralkyl group, and XI and X2 represent a halogen. A method for producing a linear polymer having a polymerization unit represented by the formula (I) and a molecular weight of 1,000 to 2,000,000 (wherein R is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group). Xl represents a group, and X2 represents a halogen.)