JPS61176614A - Alpha-halogenoisopropenylcumene unit-containing polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled polymer, having good reactivity, and suitable for ion exchange resins, etc., by polymerizing diisopropylbenzene and if desired an anionically polymerizable monomer, and adding a hydrogen halide to the resultant polymer. CONSTITUTION:(A) Diisopropylbenzene, in a relatively low concentration if a gelatinous material is not desired, and if desired (B) another anionically polymerizable monomer, e.g. styrene, in the presence of a catalyst, e.g. organolithium compound, in a diluent to give an alpha-halogenoisopropenylcumene unit-containing polymer. (C) A hydrogen halide is then introduced into the polymer at room temperature while stirring to afford the aimed polymer, having preferably >=1,000mol.wt., and expressed by the formula (X is halogen.)

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polymer containing α-halogenoiisopropenylcumene units useful as a reactive polymer and a method for producing the same.

[Conventional technology]

Many polymers are known as reactive polymers, and among them, chloromethylated polystyrene is used for ion exchange resins and other purposes because of its good reactivity.

[Problem that the invention seeks to solve]

Although chloromethylated polystyrene is an extremely useful reactive polymer, it is desired to develop a reactive polymer with different properties.

[Means for solving problems]

The present inventors conducted research to achieve the above object and finally arrived at the present invention.

That is, in the present invention, in the general formula C, X represents a halogen atom. ) A polymer containing an α-halogenoipropenylcumene unit and a method for producing the same.

The polymer of the present invention may have the above-described α-nologenoisobropenylcumene unit, and may also contain other monomer units.

Other monomer units include styrene, styrene derivatives such as α-methylstyrene and p-methylstyrene, dienes such as butadiene and isoprene, and those with polar groups such as N,N-dimethylacrylamide and methyl methacrylate. Examples include monomers having various carbon-carbon double bonds. Note that two or more types of these may be used.

Further, as long as the α-halogenoinpropenylcumene unit is contained, the ratio with other monomer units may be arbitrary.

Further, the molecular weight of the polymer of the present invention is not particularly limited, but if moldability as a polymer is taken into consideration, it is usually 1,
000 or more, preferably about 5,000,000 to 1,000,000.

The polymer of the present invention is preferably produced by adding hydrogen chloride to a diisopropenyl polymer obtained by anionically polymerizing diimpropenylbenzene, optionally with other anionically polymerizable monomers. be done.

The method for producing the diisopropenylbenzene polymer used here is not particularly limited except for anionic polymerization, and polymerization using ordinary organic lithium and/or organic sodium may be used. Conditions such as the polymerization temperature, the concentration of the catalyst, the diluent, and the co-catalyst may be determined as appropriate depending on the desired reaction rate, molecular weight, etc.

Note that since diisopropenylbenzene is a difunctional monomer, it may gel during the reaction, so if you do not like a gelatinous material, use a relatively low concentration of diisopropenylbenzene and react at a relatively low temperature. Preferably, the polymerization is carried out at Japanese Unexamined Patent Application Publication No. 1983-1982 describes a method for producing diimpropenylbenzene polymers and copolymers thereof that do not form gelled products.
No. 207905 is known, and it is also possible to polymerize under the conditions disclosed therein. What is important in producing this diimpropenylbenzene-containing polymer is that the reaction be carried out under conditions that will yield a polymer having an impropenyl group.

In the present invention, the diisopropenylbenzene-containing polymer obtained in the above reaction is usually dissolved or dispersed in a halogenated hydrocarbon or aromatic hydrocarbon and is brought into contact with a hydrogen halide to form α-halogenoisopropenylcumene. It can be a polymer containing units. The reaction between hydrogen halide and isopropenyl group is extremely fast, and usually the reaction can be easily carried out quantitatively simply by introducing hydrogen halide under stirring at room temperature. After the reaction is completed, unreacted hydrogen halide is removed and, if necessary, the used solvent is removed to obtain a polymer having α-halogenoisopropenylcumene units.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 50ml of sufficiently dried toluene, 10ml of m-diisopropenylbenzene, and 1frLt of diglyme were added to a 200fL/round bottom flask, and the mixture was cooled to -70°C with stirring. While charging ethylene gas at [2/min], butyl lithium (10 wt%, hexane solution) was added 1-
The reaction was carried out at 70°C for 2 hours, and then methanol 1- was added to stop the reaction.

After the temperature was raised to room temperature, the mixture was filtered and further poured into methanol for precipitation to obtain 4.89% of polydiimbrobenylbenzene. The obtained copolymer had an intrinsic viscosity of 0.72 in a toluene solution at 30°C. In addition, the obtained polymer was subjected to absorption of hydrogen at =CH2 of the impropenyl group by proton NMR (CDC1, medium) (4,8-5.
4 ppm), it was recognized that isopropenyl groups were present almost quantitatively.

The thus obtained copolymer 3.09 was mixed with chloroform 10
After dissolving in 0fnl and introducing 1 (l) of hydrochloric acid gas over 60 minutes and reacting for an additional 2 hours, excess hydrochloric acid gas and chloroform were expelled with a nitrogen stream, and the mixture was vacuum-dried at room temperature. The yield was 3.6 g. , it can be estimated that an addition reaction occurs in a quantitative manner.When proton NMR of this copolymer was measured, 4,8 S5.4, which was observed in the original polymer, was detected.
The absorption attributed to =CH,2 of ppm is hardly detected, and the absorption attributed to -CH is also not observed, and the absorption attributed to -CH3 is large, and the isopropenyl group is α
- It was confirmed that it was a chloroisopropenyl group. In addition, elemental analysis (C73,96wt%, H7,65w
t%, C1l 18.16wt%).

Example 2 In Example 1, m-diimpropenylpenzeylOm
4.3 g of diisopropenylbenzene-containing copolymer (intrinsic viscosity 1.1
) was obtained. The content of diisopropenylbenzene units in this copolymer was determined by proton NMR to be 42 mol %.

1 g of this copolymer was dissolved in 100 g of chloroform, 10 g of hydrogen bromide was introduced over 60 minutes, and the mixture was further stirred for 2 hours to react. Next, after removing hydrogen bromide and chloroform, it was vacuum dried at room temperature.

In the copolymer obtained here, proton NMR shows =CH2
No absorption attributed to C73 was observed, and elemental analysis showed C73,
16wt%, H5, 83wt%, B r 2o, 96
It was wt%. Therefore, it is estimated that .

〔Effect of the invention〕

By carrying out the method of the present invention, it is possible to efficiently obtain the polymer of the present invention useful as a reactive polymer, which is industrially valuable.

Claims (1)

[Claims] 1. A polymer containing an α-halogenoiisopropenylcumene unit represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, X represents a halogen atom) 2. A general formula characterized by adding halogen hydrogen to a diisopropenylbenzene polymer obtained by anionically polymerizing isopropenylbenzene, optionally with other anionically polymerizable monomers, ▲Mathematical formula, chemical formula, There are tables, etc. ▼ (In the formula, X represents a halogen atom.) A method for producing a polymer containing an α-halogenoisopropenylcumene unit represented by the following.