A kind of preparation method of halogenated polymer

Abstract

The invention provides a method for preparing a halogenated polymer. The method comprises the following steps: a) a polymer and a halogenation agent are contacted under existence of an organic solvent and an initiator, partial hydrogen atoms in the polymer are substituted by halogen atoms to obtain a halogenation polymer solution containing halogen hydride and the initiator; and b) the halogenation polymer solution obtained in the step a) and alkali lye are fully mixed under supersonic wave effect to remove halogen hydride and the initiator. According to the method, dehalogenation and discoloration of the halogenated polymer product in a subsequent drying process are effectively inhibited; technical condition and process are simple and easy, and the pure halogenated polymer product which is not easy to fad is provided.

Description

technical field

[0001] The present invention relates to the field of preparation of halogenated polymers. Background technique

[0002] Brominated isobutylene and p-methylstyrene copolymer (BIMS) is a new elastomer material with vulcanization activity and better overall performance than brominated butyl rubber due to the fully saturated structure of the main molecular chain. When preparing halogenated rubber such as halogenated isobutylene / p-methylstyrene copolymer by solution polymerization, a halogenated polymer solution containing hydrogen halide and initiator is produced. Usually neutralized by aqueous alkali solution, washed with water, and dried to obtain dehydrated particles (containing <10-20wt% water). In the research, it is found that whether the halogenated polymer product is dried in an open mill (110°C) or vacuum-dried in a vacuum oven without heating, as long as the water content in the rubber drops to a certain level, the halogenated rubber will Discolora...

Examples

Embodiment 1

[0027](1) Fix the 1000mL glass three-necked flask equipped with a strong constant speed stirring device in an ultrasonic cleaner, add 40g of prepared isobutylene / p-methylstyrene copolymer in the three-necked flask, and then add n-hexane to prepare a concentration of 10wt % glue. Add 1.5 mol% liquid bromine, mix and stir for 1 minute, add 0.08 g of azobisisoheptanonitrile, and carry out bromination at 56°C. After 12 minutes, the red color of the glue disappeared, and the bromination reaction was completed. Quickly adopt glass sampling tube to carry out sampling, to wait for the hydrogen bromide content in the glue solution to be analyzed by nuclear magnetic resonance spectroscopy, and adopt the infrared spectrometer to measure the content of the initiator in the glue solution.

[0028] Immediately add 60mL of 1wt% NaOH aqueous solution to the three-necked bottle, turn on the switch of the ultrasonic cleaner (frequency 60KHz), adjust the heating temperature adjustment knob of t...

Embodiment 2

[0033] (1) Fix the 1000mL glass three-necked flask equipped with a strong constant speed stirring device in an ultrasonic cleaner, add 40g of prepared isobutylene / p-methylstyrene copolymer in the three-necked flask, and then add n-hexane to prepare a concentration of 10wt % glue. Add 1.7 mol% liquid bromine, mix and stir for 1 minute, add 0.10 g of azobisisoheptanonitrile, and carry out bromination at 56°C. After 12 minutes, the red color of the glue disappeared, and the bromination reaction was completed. Quickly adopt glass sampling tube to carry out sampling, to wait for the hydrogen bromide content in the glue solution to be analyzed by nuclear magnetic resonance spectroscopy, and adopt the infrared spectrometer to measure the content of the initiator in the glue solution.

[0034] Immediately add 40mL of 1wt% Na to the three-neck flask 2 CO 3 For aqueous solution, turn on the switch of the ultrasonic cleaner (frequency 80KHz), adjust the heating temperature adjustment ...

Embodiment 3

[0039] (1) A 1000mL glass three-necked flask equipped with a powerful constant-speed stirring device is fixed in an ultrasonic cleaner, and 40 g of the prepared isobutylene / p-methylstyrene copolymer is added to the three-necked flask, and then cyclohexane is added to form a concentration of 10wt% glue solution. Add 2.0 mol% liquid bromine, mix and stir for 1 minute, add 0.12 g of azobisisoheptanonitrile, and brominate at 56°C. After 12 minutes, the red color of the glue disappeared, and the bromination reaction was completed. Quickly adopt glass sampling tube to carry out sampling, to wait for the hydrogen bromide content in the glue solution to be analyzed by nuclear magnetic resonance spectroscopy, and adopt the infrared spectrometer to measure the content of the initiator in the glue solution.

[0040] Immediately add 80mL of 1wt% KOH aqueous solution to the three-necked flask, turn on the switch of the ultrasonic cleaner (frequency 120KHz), and ultrasonically disperse for...

technical field

[0001] The present invention relates to the field of preparation of halogenated polymers. Background technique

[0002] Brominated isobutylene and p-methylstyrene copolymer (BIMS) is a new elastomer material with vulcanization activity and better overall performance than brominated butyl rubber due to the fully saturated structure of the main molecular chain. When preparing halogenated rubber such as halogenated isobutylene / p-methylstyrene copolymer by solution polymerization, a halogenated polymer solution containing hydrogen halide and initiator is produced. Usually neutralized by aqueous alkali solution, washed with water, and dried to obtain dehydrated particles (containing <10-20wt% water). In the research, it is found that whether the halogenated polymer product is dried in an open mill (110°C) or vacuum-dried in a vacuum oven without heating, as long as the water content in the rubber drops to a certain level, the halogenated rubber will Discolora...

Examples

Embodiment 1

[0027](1) Fix the 1000mL glass three-necked flask equipped with a strong constant speed stirring device in an ultrasonic cleaner, add 40g of prepared isobutylene / p-methylstyrene copolymer in the three-necked flask, and then add n-hexane to prepare a concentration of 10wt % glue. Add 1.5 mol% liquid bromine, mix and stir for 1 minute, add 0.08 g of azobisisoheptanonitrile, and carry out bromination at 56°C. After 12 minutes, the red color of the glue disappeared, and the bromination reaction was completed. Quickly adopt glass sampling tube to carry out sampling, to wait for the hydrogen bromide content in the glue solution to be analyzed by nuclear magnetic resonance spectroscopy, and adopt the infrared spectrometer to measure the content of the initiator in the glue solution.

[0028] Immediately add 60mL of 1wt% NaOH aqueous solution to the three-necked bottle, turn on the switch of the ultrasonic cleaner (frequency 60KHz), adjust the heating temperature adjustment knob of t...

Embodiment 2

[0033] (1) Fix the 1000mL glass three-necked flask equipped with a strong constant speed stirring device in an ultrasonic cleaner, add 40g of prepared isobutylene / p-methylstyrene copolymer in the three-necked flask, and then add n-hexane to prepare a concentration of 10wt % glue. Add 1.7 mol% liquid bromine, mix and stir for 1 minute, add 0.10 g of azobisisoheptanonitrile, and carry out bromination at 56°C. After 12 minutes, the red color of the glue disappeared, and the bromination reaction was completed. Quickly adopt glass sampling tube to carry out sampling, to wait for the hydrogen bromide content in the glue solution to be analyzed by nuclear magnetic resonance spectroscopy, and adopt the infrared spectrometer to measure the content of the initiator in the glue solution.

[0034] Immediately add 40mL of 1wt% Na to the three-neck flask 2 CO 3 For aqueous solution, turn on the switch of the ultrasonic cleaner (frequency 80KHz), adjust the heating temperature adjustment ...

Embodiment 3

[0039] (1) A 1000mL glass three-necked flask equipped with a powerful constant-speed stirring device is fixed in an ultrasonic cleaner, and 40 g of the prepared isobutylene / p-methylstyrene copolymer is added to the three-necked flask, and then cyclohexane is added to form a concentration of 10wt% glue solution. Add 2.0 mol% liquid bromine, mix and stir for 1 minute, add 0.12 g of azobisisoheptanonitrile, and brominate at 56°C. After 12 minutes, the red color of the glue disappeared, and the bromination reaction was completed. Quickly adopt glass sampling tube to carry out sampling, to wait for the hydrogen bromide content in the glue solution to be analyzed by nuclear magnetic resonance spectroscopy, and adopt the infrared spectrometer to measure the content of the initiator in the glue solution.

[0040] Immediately add 80mL of 1wt% KOH aqueous solution to the three-necked flask, turn on the switch of the ultrasonic cleaner (frequency 120KHz), and ultrasonically disperse for...