JPS60262806A - Halogen-terminated liquid diene polymer and its production - Google Patents

Abstract

PURPOSE:The titled polymer which can form a cured product excellent in rubber elasticity and dynamic properties by reaction with an epoxy resin, an organic polyisocyanate compound, or the like, having a specified structural formula. CONSTITUTION:A halogen-terminated liquid diene polymer of formula I (wherein X is a halogen and n is 6-450). A conventional liquid diene polymer shows fluidity at room temperature and, when cured, it forms a three-dimensional network structure which shows physical properties like those of a vulcanized rubber. Though it is useful as a cross-linking agent for polymers containing a long- chain diamine or double bonds, the rubber elasticity or physical properties of such a cured product has been unsatisfactory. By the incorporation of terminal halogen atoms, the diene polymer can form a cured product excellent in rubber elasticity and dynamic properties and used as a resin modifier, raw material for a cured product or the like. This polymer is produced by reacting a hydroxyl group-terminated liquid diene polymer of formula II with a halogen compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid diene polymer having a halogen at its terminal and a method for producing the same.

A liquid diene polymer is a polymer that has fluidity at room temperature, forms a three-dimensional network structure through appropriate chemical treatment, such as curing treatment, and exhibits the same physical properties as ordinary vulcanized rubber. Until now, liquid diene polymers having a halogen inside the molecule have been known.

However, although this polymer is useful as a crosslinking agent for long-chain diamines and polymers with double bonds, when it is three-dimensionally crosslinked, free chains are generated at the ends, and the rubber elasticity of the resulting cured product is The disadvantages were that it had poor performance and dynamic properties.

The object of the present invention is to provide a novel liquid diene polymer and a method for producing the same, which can overcome these conventional drawbacks and provide a cured product with poor physical properties.

That is, the present invention firstly general formula % formula % (1) [In the formula, X represents a halogen, and n represents 6 to 450.

] It provides a liquid diene-based polymer having a halogen at the end represented by the general formula % () [wherein n represents 6 to 450]. ] General formula % formula % (1) characterized by reacting a halogen compound with a liquid diene polymer having a hydroxyl group at the terminal represented by [wherein, X represents a halogen, and n represents 6 to 450] show.

] The present invention provides a method for producing a liquid diene polymer having a halogen at the end represented by the following.

In the compound represented by the above general formula (1), X is a halogen (fluorine, chlorine and pentabromine) as described above.

iodine). Moreover, n has shown 6-450.

The first aspect of the present invention is thus a novel liquid diene polymer having halogens at both ends of the molecule, and a cured product having excellent rubber elasticity and dynamic properties can be obtained by curing treatment.

The first novel liquid diene polymer of the present invention can be produced by various methods, and for example, can be produced by the second method of the present invention described below.

That is, it can be produced by reacting a halogen compound with a liquid diene polymer having a hydroxyl group at the terminal represented by the above general formula (n). General formula C above
In the compound represented by I+), n is 6 to 450.

Further, the halogen compound may include a variety of commonly used halogen compounds. For example, hydrogen bromide (HBr),
Hydrogen halides such as hydrogen chloride (HCI), hydrogen fluoride (HF), and hydrogen iodide (Hl); phosphorus trihalide,
Examples include phosphorus halides such as phosphorus pentahalide.

Specifically, the phosphorus trihalide is PB,...
PCl3, etc., and P as a phosphorus pentahalide.
B.S.

Examples include PCl5. Further, as the phosphorus halide, a compound of phosphorus and bromine can also be used. Furthermore, halogen compounds include chlorobenzene, bromobenzene, and chlorotoluene.

Aryl halides such as bromotoluene; alkyl halides such as methyl chloride, methyl bromide, carbon tetrachloride, carbon tetrabromide; thionyl chloride.

Examples include thionyl halides such as thionyl bromide; acid halides such as acetyl chloride and acetyl bromide. Among these, thionyl halides such as thionyl chloride and thionyl bromide are particularly preferably used.

The reaction between the compound represented by the above general formula (II) and a halogen compound is usually carried out at a temperature of -10 to 200°C, preferably 0 to 100°C, and a pressure of 1 to 20 atm, preferably 1 to 10
It is carried out at atmospheric pressure for 0.1 to 24 hours, preferably for 1 to 12 hours.

Further, although this reaction proceeds even in the absence of a solvent, it is preferable to use a solvent. Examples of the solvent used in this case include chlorine, chloroform, dimethylformamide, acetonitrile, and the like, and two or more of the above solvents can also be used in combination. Other stabilizers such as φ-quinone, hydroquinone, hydroquinone monomethyl ether, BHT, dinitrophenol, nitrosophenol, etc. may be added if necessary.

In this way, a novel liquid diene polymer having a halogen at the terminal represented by the above general formula (1) can be produced.

The liquid diene polymer of the present invention thus obtained can be reacted with an epoxy resin, an organic polyisocyanate compound, etc. to produce a cured product with excellent rubber elasticity and dynamic properties.

Therefore, the liquid diene polymer of the present invention can be effectively used as a resin modifier or a raw material for a cured product.

In addition, a liquid diene polymer having a halogen at the end represented by the general formula (1) obtained by reacting a halogen compound with a liquid diene polymer having a hydroxyl group at the end represented by the general formula (It) as shown in Ujigami. A liquid diene polymer having an amino group at the end can be produced by reacting the polymer with ammonia or an amine. A cured product obtained by reacting this liquid diene polymer having an amino group at its terminal with an epoxy resin, an organic polyisocyanate compound, etc. has better water resistance, chemical resistance, etc.

Next, examples of the present invention will be shown.

Example 1 A hydroxyl-terminated liquid polybutadiene (number average molecular weight 2800°, hydroxyl group content 0
．． 79 +weq/g, manufactured by Idemitsu Petrochemical ■.

Poly bd R-45HT) 53.4g, 600mj of chloroform as a reaction solvent! 4 g of pyridine was added as a reaction aid, and the mixture was cooled to 5°C. Then add l Omj! to this solution. 5.7 g of thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd., special grade) diluted with chloroform was added dropwise over 30 minutes. Thereafter, the reaction was carried out for 2 hours while the temperature was maintained at 5°C, and the reaction was further carried out for 6 hours under refluxing of chloroform. After the reaction, 100m7! of distilled water was added and stirred to remove unreacted thionyl chloride. Next, this reaction solution was transferred to a 21 separatory funnel, about 600 m
Washing was carried out twice by adding 1 liter of distilled water. After separation, the solvent was removed to obtain 40.3 g of a reaction product.

The analysis results of the physical properties of this reactant are shown below.

Hydroxyl group equivalent Q, 08 @eq/g (by acetylation method) Chlorine content 1.87 Heavy-duty viscosity 125 boids/15°C Elemental analysis carbon 87.0%, hydrogen 10.9%.

Oxygen: 0.3%, Chlorine: 1.87% Furthermore, as a result of infrared absorption spectrum analysis (IR analysis), it was recognized that absorption by hydroxyl groups at 3200 to 3600 cm-' had disappeared.

Example 2 Example 1 except that 10.0 g of thionyl chloride was used instead of thionyl chloride in Example 1.
A reaction product was obtained in the same manner as above.

The analysis results of the physical properties of this reactant are shown below.

Hydroxyl group equivalent Q, 03 n+eq/g (by acetylation method) Bromine content 4.12% by weight Viscosity 230 boids/15°C Elemental analysis Carbon 85.0%5 Hydrogen 10.6%.

Oxygen 0.3%, Bromine 4.1% Also, as a result of IR analysis, 3200~3600c+a-'
It was observed that the absorption by hydroxyl groups in .

Application example Bromine-terminated liquid polybutadiene 1 obtained in Example 2 above
Add 9g of methylated tetraethyltetramine to 00g,
A cured product was obtained by mixing and stirring to defoam. This cured product showed good elasticity.

Claims (2)

[Claims] (1) General formula % formula % [In the formula, X represents a halogen, and n represents 6 to 450. ] A liquid diene polymer having a halogen at the end represented by: (2) General formula % formula % [wherein n represents 6 to 450]. ] General formula % formula % characterized by reacting a halogen compound with a liquid diene polymer having a hydroxyl group at the terminal represented by [Formula, X represents a halogen and n represents 6 to 450]. ] A method for producing a liquid diene polymer having a halogen terminus represented by: