JPS59182808A - Functional copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled novel copolymer, capable of giving a high polymer, etc. having improved complex forming ability, useful as a metal removing agent, and further useful as a flame retardant high polymer, by copolymerizing a styrene derivative containing dihalogenoethyl groups with another vinyl monomer. CONSTITUTION:(A) A monomer of formula I (A is H, 1-10C alkyl or aryl, etc.; X1 and X2 are halogen), e.g. 3-(1,2-dibromethyl)styrene, is copolymerized with (B) a monomer of formula II [Y and Z are H or 1-10C (halogenated) hydrocarbon, halogen or cyano group, etc.], preferably styrene, to give the aimed linear copolymer consisting of polymerization units of formulas III and IV having 1,000-2,000,000mol.wt. The component (A) is preferably obtained by reacting divinylbenzene with a halogenating agent prepared by inactivating a halogen molecule.

Description

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

Conventionally, many styrene derivatives have been developed and synthesized, and are widely used in the synthesis of functional polymers. For example, cyanostyrene and aminostyrene are easily polymerized by radical polymerization to provide polymers in which each rod functional group is dissolved.

Just like that, a styrene derivative with a halogen atom and L-tl
d:, chlorostyrene, bromostyrene, chloromethylstyrene, ξ-(2-bromoether)styrene, and the like are known. Many copolymers of these compounds and other vinyl monomers are known, and a copolymer of styrene B'lk having a 1,2-dino logenoethyl group and other vinyl monomers is known in this field. Not known at all.

As a result of various studies on functional polymer compounds that detect alkyl groups, the present inventors have found that:
We have discovered a novel functional co-1F combination shown below.

The copolymer according to the present invention has a structural formula (I) and a structural formula (II).
) Molecules ytoooo to 2 consisting of polymerized units represented by
．． 000,000 linear copolymer.

CI) (TI) (wherein A, ij: hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, XI and
2 represents halogen. Y and Z are hydrogen, hydrocarbon group (carbon number 1 to 10), ... rogenated hydrocarbon group (carbon number 1 to 10), no-logon, cyan group, hydroxyl group, 0O
OR, (R is hydrogen or a hydrocarbon group with 1 to 10 carbon atoms), coR2 (Ra is a hydrocarbon group with 1 to 10 carbon atoms), 000 horse (R is a hydrocarbon group with 1 to 10 carbon atoms) )
Katsutaba 0ONH bird (R4 is hydrogen, carbon number is 1 to io
(hydrocarbon group).

In structural formula (1), a preferable embodiment of xi and xZ is a combination of chlorine, bromine, and iodine, which are the same and different in size. -1: The preferable positional relationship between the main group and the 1,2-dino-lognoethyl group is the meta position, the ξ position, or a mixture thereof.

In structural formula (TI), Y is hydrogen or a methyl group, Z is a phenyl group, a cyano group, a chloromethylphenyl group, or a halogen i k 1.0OOR.

aoR2,0COJ113. coNnn, 4(几H,
112+ R3+ R4 is water cable or carbon number 1 to 10
An electron-withdrawing group such as a hydrocarbon group) is preferred. Of course, copolymers containing several types of polymerized units (II) are also included in the scope of the present invention.

There is no limit to the molar fraction of polymerized units (I) and (It), but
Generally 17+2, each with a mole ratio of 10 to 98 molar. Furthermore, the moiety represented by the structural formula (I) is 20 to 80 mol %. However, as long as the properties of the copolymer are not significantly changed, a small amount of a third component other than the polymerized unit (I) and (I) may be included in the copolymer.

The molecular weight of the copolymer in the present invention is 1000 to 2,
000,000, but more preferably 10,000
2,000,000.

The copolymer of the present invention can be obtained by copolymerizing a monomer represented by the structural formula (g) and a monomer represented by the structural formula (ii).

OI(2=OH (t)) (In the formula, human represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and XI and X2 represent a halogen. Y and Z represent hydrogen or a hydrocarbon group. (1 to 10 carbon atoms), ... rogenated hydrocarbon group (1 to 10 carbon atoms), ... rogen, cyan group, COO 几+ (R1 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms) ,coI(2
(x is a hydrocarbon group having 1 to io carbon atoms), ocon,,
(n3 is a hydrocarbon group with a carbon number of 1 to 10)
NHR4 (R4 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms).

The monomer represented by the structural formula can be obtained, for example, by reacting a substituted product of divinylbenzene with a halogenating agent that has inactivated the halogen molecule.

Examples of monomers represented by the structural formula - include styrene, methylstyrene, diphenylethylene, ethylstyrene,
Dimethylstyrene, vinylnaphthalene, vinylphenanthrene, vinylmesityrene, 3.4.6-) Hydrocarbon compounds of IJ dimethylstyrene; chlorstyrene, methoxystyrene, bromustyrene, anostyrene, fluorostyrene, dichlorostyrene, chloromethylstyrene, Styrene meter conductors such as trifluorostyrene and trifluoromethylstyrene: Acrylonitrile derivatives such as acrylonitrile, methacrylonitrile, and α-acetoxyacrylonitrile Niacrylic acid, methacrylic acid; Methyl acrylate, lauryl acrylate, chloromethyl acrylate, acetoquine acrylic acid Acrylic acid esters such as ethyl; Methacrylic acid esters such as cyclohexyl methacrylate; Diethyl maleate, diethyl fumarate; Vinyl ketones such as methyl vinyl ketone and ethyl isopropenyl cutone; Vinylidene compounds; acrylamide conductors such as acetamide, methacrylamide, and N-phenylacrylamide; fatty acid vinyl derivatives such as vinyl acetate, vinyl butyrate, and vinyl caprate.

Among these, Y and Z are hydrogen, ano group, ri or O
ON)]2 is more preferred.

The polymerization method for producing the copolymer of the present invention using monomers represented by structural formulas (5) and (5) is not particularly limited, and polymerization by heating is also sufficient. In many cases, it is preferable to use magic agents. Examples of polymerization initiators used include acyl peroxides such as benyl steel oxide and lauroyl peroxide, and azonitrile compounds such as azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylmaleronitrile). '4, peroxides such as ditertiary butyl peroxide, dicumyl peroxide, and methyl ethyl ketone peroxide; hydroperoxy Ps such as cumene hydroperoxide and tertiary hydroperoxy P;

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 penkune, normal hexane, normal heptane, and normal octane, alcohols such as methanol, ethanol, and isopropyl alcohol, acetone, methyl ethyl ketone, and diethyl ketone. ketones, diethyl ether, methyl ethyl ether, sifthyl ether, dioxane, tetrahydrofuran and other ethers, benzene, toluene, xylene and other aromatic hydrocarbons, ethyl formate, ethyl acetate, butyl acetate and other esters, dimethyl Appropriate liquids such as amides such as formamide and dimethylacetamide, aliphatic halides such as chloroform, methylene chloride, and dichloroethane, aromatic halides such as chlorobenzene, and dimethyl sulfoxide can also be used. 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 one halogen on each adjacent carbon. It has an alkyl-substituted phenyl group, that is, a 1,2-dihalogenoethyl phenyl group in its side chain, and can be converted into various functional groups through various reactions, making it useful as a functional polymer. For example, the EJ ability is to generate a polymer having an anion exchange ability through a reaction with a nitrogen compound, or to generate a polymer that has a chelating ability to iminodiacetic acid seed rice.

In this case, it is also possible to synthesize a similar polymer using a copolymer of alkyl-substituted styrene having one halogen atom, such as Gular (2-bromoethyl) styrene or chloromethylstyrene. However, there are very large qualitative differences in the performance of the synthesized polymers. For example, in chelating active molecules with large iminodiacetic acid groups, there are significant differences.

1. When iminodiacetic acid groups are introduced into a polymer produced from 2-dihalogenoethylstyrene, the iminodiacetic acid groups become 2
A series of side chains are generated. This is indicated by the following 4fi\ construction formula (V).

On the other hand, when iminodiacetic acid groups are introduced into a polymer produced from chloromethylstyrene, for example, the following structural formula (6) is obtained.

Here, when comparing the side chains of structural formulas (V) and (2), (
It can be seen that V) has a greater ability to form complexes with various metals, and that the chelate polymer synthesized from the copolymer of the present invention is very useful as a metal removing agent.

In fact, since the copolymer of the present invention has two halogen atoms on one button on the side, it is also useful as a flame-retardant madder molecule.

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

Example 1 8.70R of 3-(1,2-
After purging the inside of the ampoule tube with nitrogen, the tube was sealed. After immersing this in a 90°C water bath for 24 hours, the sealed tube was broken and the solidified contents were taken out. After washing with methanol and vacuum drying, the weight was measured to be 11.723 (yield 99).
%)Met. The elemental fractionation value 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) 0; 53.3
5 (5343) H; 4.90 (4,75) Tl
r; 41.75 (41,82) Infrared absorption spectrum (crn-re3020 .2970 .1600 .1510 .1
480. 1215. In the 800.690 infrared absorption spectrum, the peak attributable to the dust element-carbon 2111' bond completely disappeared, and the elemental analysis and yield indicated that the solid obtained was 3-(1,2-dibromo). It was concluded that it was a copolymer of ethyl)styrene and styrene.

The molecular weight of this product was measured by gel nomeation chromatography using polystyrene as a calibration curve, and the molecular weight was found to be 1.200,000.

Example 2 3-(1,2-dibromoethyl)styrene [4
The reaction and operation were carried out in exactly the same manner as in Example except that -(1,2-dibromoethyl)styrene was used. The yield of the obtained solid was 11.60 g (98%), and the elemental analysis values and main peaks in the infrared absorption spectrum were as follows.

Elemental analysis value (the value in parentheses represents the theoretical value) 0; 53.3
7(53,43)H:4.87(4,75)B
r; 41.76 (41,82) Infrared absorption spectrum (cm-1) 3020. 2910. 1600. 1510. 1
430. 1230. 835.695 Furthermore, the molecular weight was measured in the same manner as in Example 1 and found to be 1,100,000.

Examples 3 to 11 Copolymerization of the monomer represented by the structural formula (4) in the row I and the sheep's body represented by the structural formula - was carried out by the same method as in Example 1, and the obtained copolymer Elemental analysis and infrared absorption spectrum measurements were performed on the material. The results are shown in Table 1.

According to these results, the obtained copolymerized 4Aζ could be included in the first frame of the patent N'N + request. ],,] 2-dibromoethylstyrene, 1.80 g of styrene, 10.0 g of m-xylene, and 0.10, ... of azobisisobutyronitrile were uniformly combined, and this was combined. 3f)m/! The mixture was injected into an ampoule tube, and after the inside of the ampoule tube was air-filled, the tube was controlled. After immersing this in a 90°C water bath for 24 hours, the sealed tube was broken and the solidified contents were taken out.

This combination of 111 and 2
00 ml of 4[21] flask, then add 120 g of iminodiacetic acid ethyl ester to 100 m6' of ethanol solution (add 100 m6' of ethanol solution at 70 ° C.
-iI Continued slow stirring.

50 g of purified water with 4.0 g of sodium hydroxide dissolved in it
m/+ was added and stirring was continued for 5 hours at 90°C.

After cooling and washing with water, the metal removal ability was examined as shown in the figure.

Aqueous solution II containing 100q of famous metals by dissolving divalent Cu chloride and trivalent Fe chloride in pure water! prepared. 5.0 g of the copolymer synthesized by the above procedure was added to this aqueous solution.
was added, and after immersion for 24 hours, the amount of metal ions remaining in the aqueous solution was measured, and both Ou and Fe were 0.1 mg or less.

Patent applicant: Asahi Kasei Kokuri Co., Ltd.

Claims (1)

[Scope of Claims] (1) A molecular weight of 2,000,00 to 2,000,000 consisting of polymerized units represented by the following structural formulas (D and (Tf))
Linear copolymer of 0 H2X2 CI) (TI) (wherein A represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and Xl and X2 represent a halogen. Y and Z are Hydrogen, hydrocarbon group (1 to 10 carbon atoms),
No-logenated hydrocarbon group (1 to 10 carbon atoms), no-rogen, cyano group, hydroxyl group, C0OR, (rL is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), 0QR2 ('
R2 is a hydrocarbon group having 1 to 10 carbon atoms)ocoTL3(
4 is a hydrocarbon group having 1 to 10 carbon atoms) or C0NHR
4 (R, represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms). (2) Monomer and structural formula shown in the structural formula (g) of the manure■
(4) A method for producing a copolymer according to claim 1, characterized by copolymerizing a monomer represented by group, aryl group or aralkyl group, XI and X2 represent halogen.
0), halogen, cyan group, 0OOR, (11, is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), 0011. ,
(R2 is a hydrocarbon group having 1 to 10 carbon atoms), 00011
3 (R, is a hydrocarbon group having 1 to 10 carbon atoms) -1 or 0
ONHR4 (R represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms).