JPS614707A - Amino group-terminated liquid diene polymer and its production - Google Patents

Abstract

PURPOSE:The titled polymer improved in water resistance and chemical resistance and being lowly viscous and useful as a modifier for an epoxy resin or the like or a starting material for a cured product or the like, having an amino group on each molecular end. CONSTITUTION:An amino group-terminated liquid diene polymer of formula I (wherein n is 6-450). When compared with a conventional liquid diene polymer, this polymer is improved in water resistance and chemical resistance and is lowly viscous. For example, it can form a cured product excellent in water resistance and chemical resistance when it is added to, for example, an epoxy resin. In addition, it can eliminate a disadvantage of increasing the viscosity when it is reacted with an organic polyisocyanate compound or the like to produce a polyurethane composition. The polymer of formula I can be produced by reacting a halogen-terminated liquid diene polymer of formula II (wherein X is a halogen and n is 6-450) with ammonia or an amine.

Description

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

Liquid diene polymers are fluid at room temperature, form a three-dimensional network structure through appropriate chemical treatment, such as curing treatment, and exhibit the same physical properties as ordinary vulcanized rubber. Until now, no liquid diene polymer having an amino group at the end has been known.

This liquid diene polymer, especially a liquid diene polymer having an OH group, is useful as a resin modifier, an intermediate, a raw material for a cured product, etc., but ester bonds are formed in the molecule during curing treatment etc. If it is used, it has the disadvantage of poor water resistance and chemical resistance.

Furthermore, when urethane bonds are formed within the molecule, there is also the disadvantage that the viscosity increases.

The object of the present invention is to provide a liquid diene polymer that overcomes these conventional drawbacks and an efficient method for producing the same.

That is, the present invention firstly relates to the general formula % [] [where n represents 6 to 450]. ] The second purpose is to provide a liquid diene polymer having an amine group at the end represented by the general formula %[[:] [wherein, show.

] The general formula % is characterized by reacting a liquid diene polymer having a halogen at the terminal with ammonia or an amine. ] The present invention provides a method for producing a liquid diene polymer having an amine group at the end represented by the following formula.

In the compound represented by the above general formula [I], n is 6
~450 is shown.

The first aspect of the present invention is thus a novel liquid diene polymer having amine groups at both ends of the molecule, which has improved water resistance and chemical resistance compared to conventionally known liquid diene polymers. Moreover, it has a low viscosity.

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 liquid diene polymer having a halogen at the terminal represented by the general formula [II] with ammonia or an amine.

In the compound represented by the above general formula [■], X represents halogen, ie, chlorine, bromine, fluorine or iodine, and n represents 6 to 450.

Note that the liquid diene polymer having a halogen at the terminal represented by the general formula [■] can be obtained by various methods. For example, the general formula % formula %[1[[] [wherein n represents 6 to 450]. ] It can be obtained by reacting a liquid diene polymer having a hydroxyl group at the terminal with various halogen compounds.

Here, the halogen compound may be a variety of commonly used halogen compounds. For example, hydrogen bromide (E'Br)
, hydrogen chloride (HCI), hydrogen fluoride (HF).

Examples include hydrogen halides such as hydrogen iodide (EII); phosphorus halides such as phosphorus trihalide and phosphorus pentahalide. Here, specific examples of phosphorus trihalide include PBrg, PCl3, etc., and examples of phosphorus pentahalide include PEr, , Pots, etc.

Further, as the phosphorus halide, a compound of phosphorus and bromine can also be used. In addition, halogen compounds include aryl halides such as chlorobenzene, bromobenzene, chlorotoluene, and bromotoluene; methyl chloride and methyl dibromide;

Alkyl halides such as carbon tetrachloride and carbon tetrabromide; thionyl halides such as thionyl chloride and thionyl bromide; acetyl chloride.

Examples include acid halides such as acetyl bromide.

The reaction between the compound represented by the general formula [IID] and the rogene 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 1
The reaction is carried out at 0 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.

In this way, a liquid diene polymer having a halogen at its terminal can be obtained.

In the method of the present invention, the thus obtained liquid diene polymer having a halogen at the terminal represented by the above general formula [■] is reacted with ammonia or an amine.

The amine is not particularly limited, and any of primary, secondary, and tertiary amines may be used, and any of aliphatic amines, alicyclic amines, and aromatic amines may be used. good. Specifically, for example, aliphatic primary amines such as methyl amine and ethylamine; aliphatic secondary amines such as dimethylamine, diethylamine, and dibutylamine;
Amines; aliphatic tertiary amines such as trimethylamine and triethylamine; aliphatic unsaturated amines such as allylamine and diallylamine; alicyclic amines such as cyclopropylamine and cyclobutylamine; aniline, methylaniline, benzylamine, dibenzylamine, etc. Examples include aromatic amines.

Although various amines or ammonia can be used as described above, ammonia is most preferably used.

The reaction between the compound represented by the above general formula [■] and ammonia or amine is usually carried out at a temperature of 10 to 200°C, preferably 50 to 150°C, and a pressure of 1 to 20 atm, preferably 1 to 10 atm. It is carried out for 0.1 to 24 hours, preferably 0.5 to 6 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 water, alcohol, ketone, toluene, etc., and two or more of the above solvents may be used in combination. Other stabilizers as necessary, such as p-quinone, nohydroquinone, nohydroquinone monomethyl ether, BE'l
”, dinitrophenol, nitronephenol, etc. can be added.

In this way, a novel liquid diene polymer having an amine group at the terminal represented by the above general formula [■] can be produced.

The liquid diene polymer of the present invention thus obtained can be blended with, for example, an epoxy resin to produce a cured product with excellent water resistance and chemical resistance. Also,
The liquid diene polymer of the present invention does not have the disadvantage of increased viscosity even when reacting with an organic polyincyanate compound or the like to produce a polyurethane composition.

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

Next, examples of the present invention will be shown.

Preparation Example (Preparation of chlorine-terminated liquid rubber) Hydroxyl-terminated liquid polybutadiene (number average molecular weight: 12,800°, hydroxyl group content: 0
．． 7'9 meq/g, manufactured by Idemitsu Petrochemical Co., Ltd.

Pojy bd R-45HT) 53.49, 600 ml of chloroform as a reaction solvent, and 4 g of pyridine as a reaction aid were added, and the mixture was cooled to 5°C. Then add 1 to this solution
Thionyl chloride (manufactured by Wako Tsumugi Co., Ltd., special grade) 5.79% diluted with 0M 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 was completed, 100% distilled water was added and stirred to remove unreacted thionyl chloride. Next, this reaction solution was transferred to a 21 separatory funnel and washed twice by adding about 600 g of distilled water. After separation, the solvent was removed and the reactant 40. 'I got 3g.

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

Hydroxyl group j40.08 meq/9 (by acetylation method) Chlorine content 1.87% by weight Viscosity 125 poise/15℃ elemental analysis value
Carbon 87.0% Hydrogen 10.9% Oxygen 0.3% Chlorine 1.87% Additionally, as a result of infrared absorption spectrum analysis (zR analysis), absorption by hydroxyl groups at 3200 to 36oO-1 has disappeared. This was recognized.

Production example (production of amine-terminated liquid rubber) In a 30 ml autoclave, 2.0 g of the chlorine-terminated liquid polybutadiene obtained in the above preparation example, 10 M of tositetoluene as a reaction solvent, and 0.05 potassium iodide as a reaction aid were placed in a 30 ml autoclave.
g, add 10 d of ammonia/ethyl alcohol saturated solution as ammonia, temperature 120°C 1 hour 90 minutes, pressure j
The reaction was carried out under heating and pressure at a temperature of E 4 k19/cm2. After the reaction was completed, the solvent, unreacted ammonia, etc. were removed using an evaporator. A part of the obtained reaction product was dissolved in toluene, transferred to a separating funnel, and distilled water was added to wash the reaction product. The cleaning solution was found to be neutral by test paper.

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

Chlorine content 0.3% by weight Viscosity 250 poise/15°C Elemental analysis values Carbon 87.7% Hydrogen 11.1% Nitrogen 0.7% Analysis by infrared absorption spectrum (IR analysis) 3200~
3600cm-” Amine N-I (stretching vibration 1020cm-”
cI! L-” Amine 0-N stretching vibration example Tolylene diisocyanate (2,4-)lylene diisocyanate 80% by weight, 2,6-tolylene diisocyanate 20% by weight to 10g of the amine-terminated liquid rubber obtained in the above production example. %) 0.4g, silicone antifoaming agent Q, Q
O79 was added and quickly stirred and mixed to obtain a cured product. The hardness (JIS K6301, Shore A) of this cured product was 45, and the water resistance and chemical resistance were good.

Claims (1)

[Claims] 1. General formula H_2N-(CH_2-CH=CH-CH_2)-_n
NH_2 [wherein, n represents 6 to 450]. ] A liquid diene polymer having an amino group at the end represented by: 2. General formula X-(CH_2-CH=CH-CH_2)-_nX [wherein, ] General formula H_2N-(CH_2-CH=CH-CH_2)-_n characterized by reacting ammonia or an amine with a liquid diene polymer having a halogen at the end represented by
NH_2 [wherein, n represents 6 to 450]. ] A method for producing a liquid diene polymer having an amino group at the end represented by: