JPS6137805A - Liquid, amino group-terminated diene copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer whose properties such as viscosity can be easily controlled and which gives a cured product excellent in chemical and water resistances, by reacting a specified liquid, halogen-terminated diene polymer with NG3 or an amine. CONSTITUTION:A random- or block-copolymerized liquid, halogen-terminated diene copolymer comprising 4-460 repeating units of formula I and 2-230 repeating units of formula II (wherein Y is phenyl or cyano) is reacted with NH3 or an aliphatic, alicyclic or aromatic primary to tertiary amine at 10-200 deg.C and a pressure of 1-20atm. for 0.1-24 hr in the absence or presence of a solvent (e.g., toluene) to obtain a liquid, amino group-terminated diene copolymer comprising 4-460 repeating units of formula I and 2-230 repeating units of formula II.

Description

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

Conventionally, liquid butadiene-styrene copolymers having a hydroxyl group at the end or liquid butadiene-acrylonitrile copolymers having a hydroxyl group at the end have been known, and these have been effectively used as raw materials for cured products and various intermediates. There is.

However, these copolymers have the disadvantage that when a dicarboxylic acid or the like is used as a chain extender in a curing treatment, ester bonds are formed, and the chemical resistance, water resistance, etc. of the resulting cured product deteriorates. Furthermore, when incyanate compounds or the like are used in the curing process, the viscosity becomes extremely high, resulting in low workability and extremely difficult handling.

An object of the present invention is to provide a new copolymer that solves the above problems and a method for producing the same.

That is, the present invention provides a copolymer consisting of repeating units (0H9-OH=OH-OH1 and -(-OHg-CH) (in the formula, Y represents a phenyl group or a cyano group), wherein the molecular terminal A liquid diene copolymer having an amine group (hereinafter referred to as the first invention) and a repeating unit -(-0H2-OH= OH-OH, square and one← OHg -OH+- (in the formula, Y is a phenyl group) or a cyano group), which is a repeating unit characterized by reacting ammonia or amine with a liquid diene copolymer having a halogen at the molecular end. A copolymer consisting of -OH, square and -fCH2-〇H square A manufacturing method (hereinafter referred to as the second invention) is provided.

The copolymer of the first invention has repeating units → CH* -OH= (jH-C2H4, that is, butadiene repeating units and -(-(mll -OHte (in the formula, Y represents a phenyl group or a cyano group). That is, it is a liquid diene copolymer consisting of styrene or acrylonitrile repeating units and having amine groups at both ends of the molecule.Butadiene repeating units usually have 4
It contains about 460 repeating units, and about 2 to 230 styrene or acrylonitrile repeating units. The arrangement of these repeating units is not particularly limited, and may be any one such as a random copolymer or a block copolymer.

The first invention is a novel liquid diene copolymer having amino groups at both ends of the molecule. This product also has chemical resistance due to the use of dicarboxylic acid in the hardening process.
Water resistance etc. do not deteriorate, and viscosity etc. can be easily adjusted.

Although the novel liquid diene copolymer of the first invention described above can be produced by various methods, for example, it can be suitably produced by the method of the second invention described below.

That is, the copolymer of the first invention is produced by reacting ammonia or an amine with a liquid diene copolymer comprising the above-mentioned butadiene repeating unit and styrene or acrylonitrile repeating unit and having halogen at both molecular ends. can be manufactured.

The raw material liquid diene copolymer having halogens at both ends of the molecule usually contains 4 to 460 butadiene repeating units and 2 to styrene or acrylonitrile repeating units.
It contains about 230 pieces. The copolymer may be a random copolymer, a block copolymer, or the like. Such a liquid diene copolymer having a halogen at the end is usually obtained by reacting a liquid diene copolymer having a hydroxyl group at the end with various halogen compounds.

The liquid diene copolymer having a hydroxyl group at the end is a copolymer consisting of about 4 to 460 butadiene repeating units and about 2 to 230 styrene or acrylonitrile repeating units, and has hydroxyl groups at both ends of the molecule. be. This copolymer may be a random copolymer, a block copolymer, or the like. Various halogen compounds can be used here. For example, hydrogen bromide (HBr), hydrogen chloride (UCZ),
Hydrogen halides such as hydrogen fluoride (:EIF) and hydrogen iodide (HI); phosphorus halides such as phosphorus trihalide and phosphorus pentahalide can be mentioned. Specifically, the phosphorus trihalide is PBr3, PC! , etc., and as a phosphorus pentahalide, PBr 6
e.POLg etc. Further, as the phosphorus halide, a compound of phosphorus and bromine can also be used.

Also, chlorobenzene is a halogen compound.

Aryl halides such as bromobenzene, chlorotoluene, and bromotoluene; Alkyl halides such as methyl chloride, methyl bromide, carbon tetrachloride, and carbon tetrabromide; Thionyl halides such as thionyl chloride and thionyl bromide; acetyl chloride, acetyl Examples include acid halides such as bromide.

The reaction between the liquid diene copolymer having the above two types of repeating units and a hydroxyl group at the terminal 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
~20 atm, preferably 0.1-24 at 1-10 atm
The reaction time is preferably 1 to 12 hours.

Further, although this reaction proceeds even in the absence of a solvent, it is preferable to use a solvent. Benzene, chloroform, dimethylformamide, acetonitrile, etc. can be used as the solvent. In addition, stabilizers such as p-quinone and hydroquinone may be added as appropriate.

In this way, a liquid diene-based copolymer having a norylogen at the terminal can be obtained.

In the method of the present invention, the thus obtained liquid diene copolymer having a halogen at its terminal 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, methylamine,
Aliphatic primary amines such as ethylamine; aliphatic secondary amines such as dimethylamine, diethylamine, dibutylamine; aliphatic tertiary amines such as trimethylamine, triethylamine; aliphatic unsaturated amines such as allylamine, diallylamine; cyclobutylamine.

Examples include alicyclic amines such as cyclobutylamine; aromatic amines such as aniline, methylaniline, benzylamine, and dibenzylamine.

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

The reaction between the liquid diene copolymer having a halogen at the terminal and ammonia or amine is usually carried out at a temperature of 10 to 20°C.
0°C, preferably 50-150°C, pressure 1-20 atmospheres,
Preferably under conditions of 1 to 10 atm for 3.1 to 24 hours,
It is preferably carried out for 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, hydroquinone, hydroquinone monomethyl ether, EHT,
Dinitrophenol, nitrosophenol, etc. can be added.

In this way, a novel liquid diene polymer having an amino group at the terminal can be produced.

The liquid diene copolymer of the present invention does not form ester bonds even when dicarboxylic acid, etc., which is a chain extender, is used, and a cured product having excellent chemical resistance, water resistance, etc. can be obtained. . Further, when the resin is cured by reacting with an incyanate compound, workability, handling properties, etc. are good. Therefore, by curing the liquid diene copolymer of the present invention, a cured product with improved properties can be easily produced.

Therefore, the liquid diene copolymer of the present invention can be effectively used as a raw material for a cured product and various intermediates.

Next, the present invention will be explained in detail with reference to examples.

Example 1 Liquid polybutadiene-styrene copolymer with chlorine terminals was placed in a 3001 volume autoclave. ON,) luene lQQm, potassium iodide 0.59 and ammonia-
Add 100 d of ethyl alcohol saturated solution, temperature 120
The reaction was carried out for 90 minutes at a temperature of 4 kg/cIn2. 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 and transferred to a separating funnel, and distilled water was added to wash the reaction product.

The analysis results of this reaction product are shown below.

Amine equivalent: 0.36 meq/g Chlorine content: 0.2 wt% Viscosity: 300 boids/30°C elemental analysis (wt%) Carbon: 88.5. Hydrogen: 10.2° Oxygen: 0.0. Nitrogen: 1.0 In addition, peaks at 3200 to 3600 F-1 (amine N=H stretching vibration) and 1020 F-1 (amine O-N stretching vibration) were observed in infrared absorption spectrum analysis (IR analysis). Ta.

Tolylene diisocyanate (2,4-) was added to the obtained liquid diene copolymer 10.0.9 having an amino group at the terminal.
Tolylene diisocyanate (80%) and 2.6-tolylene diisocyanate (20%) (3.3.9) and a silicone antifoaming agent (0.0079) were added and quickly stirred and mixed to obtain a liquid rubber cured product. The hardness of this material (Shore hardness (4)
) based on JIS K-6301) was 50. Also,
The weight change rate when immersed for 168 hours in hot water at 70°C is 0.1% by weight or less, and the weight change when immersed for 168 hours in 1% sodium hydroxide aqueous solution at 70°C. The rate of change was also less than 0.1% by weight.

Example 2 Reaction production was carried out in the same manner as in Example 1 except that a liquid polybutadiene-styrene copolymer having bromine at the terminal was used instead of the liquid polybutadiene-styrene copolymer having chlorine at the terminal in Example 1. I got something.

The analysis results of this reaction product are shown below.

Amine equivalent: 0.33 meq/, 9 Bromine content: 0.4 wt% Viscosity: 450 poise/30'C Elemental analysis (wt%) Carbon: 88-3, Hydrogen: 10.1.

Oxygen: 0.0. Nitrogen: 0.9 In addition, 3200-3600 cIrL in ■⇠ analysis
-” (amine N-,H stretching vibration) and 1020 cm
' (Amine C--N stretching vibration) peak was observed.

Example 3 A reaction product was produced in the same manner as in Example 1 except that a liquid polybutadiene-acrylonitrile copolymer having a chlorine terminal was used instead of a liquid polybutadiene-styrene copolymer having a chlorine terminal in Example 1. I got it.

The analysis results of this reaction product are shown below.

Amine equivalent: 0.31 meq/, 9 Chlorine content: 0.3 wt% Viscosity: 890 poise/30°C Elemental analysis value (wt%) Carbon: 84.6, Hydrogen: 10.2° Oxygen: 0.
0. Nitrogen: 4.8 In addition, 3200 to 3600 tx-” in IR analysis
(Amine N-H stretching vibration) and 1020crn-”
(Amine C--N stretching vibration) peak was observed.

Tolylene diisocyanate (80% of 2,4-tolylene diisocyanate and 20% of 2,6-)lylene diisocyanate) 2.89 and silicone-based extinguisher were added to the obtained 10-Og liquid diene copolymer having an amine group at the terminal. A foaming agent of 0.007 F was added and quickly stirred and mixed to obtain a liquid rubber cured product. The hardness of this material (Shore hardness (A)
) based on JIS K-6301] was 52. In addition, the weight change rate when immersed in hot water at 70°C for 168 hours was less than 0.1% by weight, and 1° at 70°C.
The rate of weight change when immersed for 168 hours in an aqueous solution of IJ(%) hydroxide was also 0.1% by weight or less.

Example 4 The reaction product was produced in the same manner as in Example 1 except that a liquid diene copolymer having a bromine terminal was used instead of the liquid diene copolymer having a salt at the terminal in Example 1. Obtained.

The analysis results of this reaction product are shown below.

Ami, equivalent weight 0.30 meq/7 Bromine content
0.5 wt% Viscosity 980 Boise/30°C Elemental analysis value (wt%) Carbon: 84.4, Hydrogen: 10.2° Oxygen: 0.
0. Nitrogen = 4.8 In addition, 3200 to 3600 cyrb in IR analysis
-” (Amine N-H stretching vibration) and 1020 Sol-1 (
A peak of amine C--N stretching vibration) was observed.

Claims (8)

[Claims] (1) A copolymer consisting of repeating units -(CH_2-CH=CH-CH_2)- and ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Y represents a phenyl group or a cyano group.) , a liquid diene copolymer with an amino group at the end of the molecule. (2) The copolymer according to claim 1, wherein the number of repeating units -(CH_2-CH=CH-CH_2)- in the copolymer is 4 to 460. (3) The copolymer according to claim 1, wherein the copolymer has 2 to 230 repeating units. (4) The number of repeating units in the copolymer -(CH_2-CH=CH-CH_2)- is 4 to 460, and the number of repeating units in the copolymer ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is 2 to 230. The copolymer according to claim 1, which is (5) A copolymer consisting of a repeating unit -(CH_2-CH=CH-CH_2)- and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Y represents a phenyl group and a cyano group.) , a repeating unit characterized by reacting ammonia or amine with a liquid diene copolymer having a halogen at the end of the molecule - (CH_2-CH=CH-CH_2) - and ▲ mathematical formulas, chemical formulas, tables, etc. ▼ ( A method for producing a liquid diene copolymer having an amino group at the end of the molecule. (6) The manufacturing method according to claim 5, wherein the number of repeating units -(CH_2-CH=CH-CH_2)- in the copolymer is 4 to 460. (7) The manufacturing method according to claim 5, wherein the number of repeating units ▲numerical formula, chemical formula, table, etc.▼ in the copolymer is 2 to 230. (8) There are 4 to 460 repeating units -(CH_2-CH=CH-CH_2)- in the copolymer, and 2 to 230 repeating units ▲There are mathematical formulas, chemical formulas, tables, etc.▼ in the copolymer. The manufacturing method according to claim 5, wherein the manufacturing method is: