Photochromic polymers containing spiro group and its synthetic method

Abstract

Photochromic polymers containing spiro-class radical group and synthetic method thereof are provided. The polymers consist of eight photochromic polymers formed by four spiro photochromic units polymerize with trans-dichloro bis (triphenylphosphine) platinum / palladium respectively. The synthetic method is as follows: (1) benzophenone carbonyl addition reaction; (2) photochromic units gained by cyclization reaction; (3) a Carbon-carbon triple bond that is gained by sonogashira coupling reaction; (4) terminal alkyne hydrogen that is gained by hydrolysis reaction; and (5) carrying out carbonyl addition reaction of benzophenone, carrying out to obtain photochromic units, carrying out a sonogashira coupling reaction to obtain a carbon-carbon triple bond, carrying out hydrolysis reaction to obtain terminal alkyne hydrogen and carrying out polymerization reaction. The preparation method of the photochromic polymer is simple with low preparation cost and high productivity, and has a wider range of application than the prior polymers.

Description

technical field

[0001] The invention relates to the field of organic photochromic materials, in particular to photochromic polymers containing spirocyclic groups and a synthesis method thereof. Background technique

[0002] Photochromism is the reversible change of a substance between two physical or chemical states, at least one of which is caused by light radiation, which can be expressed by the following equation:

[0003]

[0004] where A and B respectively represent two different color states of the same substance: λ 1 and lambda 2 represent two different wavelengths respectively.

[0005] The basic characteristics of photochromism are: A and B can exist stably under certain conditions; A and B have obvious color parallax. However, to realize the real application, the following conditions must be met: the two have high stability; the two have high cycle life; the absorption band is in the visible light range; the response speed is fast and the sensitivity is high....

Examples

Embodiment 1

[0045] The synthetic method of photochromic polymer 1 containing spiro group, comprises the following steps:

[0046] Step 1. Using trimethylsilylacetylene as a raw material, react with butyl lithium and 4,4'-dibromobenzophenone at -78°C under nitrogen protection conditions to generate hydroxyl-containing terminal alkyne bonds in equal amounts compound;

[0047] The reaction formula is:

[0048]

[0049] The specific operation is: add 1.67g (17mmol) TMSA to a 250ml three-necked flask, add 30ml anhydrous tetrahydrofuran, cool to -78°C, slowly add 6.5ml (15.6mmol) of 2.4M butyllithium solution dropwise, and keep warm for 30min. 4.82 g (14.2 mmol) of 4,4'-dibromobenzophenone was added. After 12 hours, deionized water and 3.7 g (14.2 mmol) of tetrabutylammonium fluoride were added. The organic layer was extracted with dichloromethane, spin-dried and passed through the column with dichloromethane:petroleum ether=3:1 to obtain a light yellow solid m=5.23g, η=98%;

[0050] The...

Embodiment 2

[0087] The synthetic method of photochromic polymer 2 containing spiro group, comprises the following steps:

[0088] Step 1. Using trimethylsilylacetylene as a raw material, under the condition of nitrogen protection at -78°C, through the reaction of butyl lithium and 4-bromobenzophenone in equal amounts to generate a hydroxyl-containing terminal alkyne bond compound;

[0089] The reaction formula is:

[0090]

[0091] The specific operation is: add 1.67g (17mmol) TMSA to a 250ml three-necked flask, add 2.4g (24mmol) TMSA to a 250ml three-necked flask, add 30ml anhydrous tetrahydrofuran, and cool to -78°C. Add 8.8ml (22mmol) of 2.4M butyllithium solution dropwise slowly, and keep warm for 30min. Add 5.22 g (20 mmol) of 4 dibromobenzophenone. After 12 hours, deionized water and 5.23 g (20 mmol) of tetrabutylammonium fluoride were added. The organic layer was extracted with dichloromethane, spin-dried and passed through the column with dichloromethane:petroleum ether=3:1 ...

Embodiment 3

[0128] The synthetic method of photochromic polymer 3 containing spiro group, comprises the following steps:

[0129] Step 1, the same as Step 1 in Example 2 to obtain a hydroxyl-containing terminal acetylenic bond compound.

[0130] Step 2, the product obtained in step 1 is dehydrated with 4,4'-biphenyldiphenol under the catalysis of pyridine p-toluenesulfonate with a mole fraction ratio of 5% through three times the equivalent of dehydrating agent trimethyl ortho acid ring-closing reaction to obtain a corresponding spiro-type photochromic unit;

[0131] The reaction formula is:

[0132]

[0133] The specific operation is: add 1.5g (5.2mmol) of bromide, 0.46g (2.5mmol) of 4,4'-biphenol, 0.07g (0.28mmol) of pyridine p-toluenesulfonate (PPTS) into the reaction tube, nitrogen Under atmosphere, 1.7 ml (15.6 mmol) of trimethyl orthoacid was added, and then 25 ml of 1,2-dichloroethane was added, and the mixture was stirred at 85° C. for 12 hours. Pass through the column with ...

technical field

[0001] The invention relates to the field of organic photochromic materials, in particular to photochromic polymers containing spirocyclic groups and a synthesis method thereof. Background technique

[0002] Photochromism is the reversible change of a substance between two physical or chemical states, at least one of which is caused by light radiation, which can be expressed by the following equation:

[0003]

[0004] where A and B respectively represent two different color states of the same substance: λ 1 and lambda 2 represent two different wavelengths respectively.

[0005] The basic characteristics of photochromism are: A and B can exist stably under certain conditions; A and B have obvious color parallax. However, to realize the real application, the following conditions must be met: the two have high stability; the two have high cycle life; the absorption band is in the visible light range; the response speed is fast and the sensitivity is high....

Examples

Embodiment 1

[0045] The synthetic method of photochromic polymer 1 containing spiro group, comprises the following steps:

[0046] Step 1. Using trimethylsilylacetylene as a raw material, react with butyl lithium and 4,4'-dibromobenzophenone at -78°C under nitrogen protection conditions to generate hydroxyl-containing terminal alkyne bonds in equal amounts compound;

[0047] The reaction formula is:

[0048]

[0049] The specific operation is: add 1.67g (17mmol) TMSA to a 250ml three-necked flask, add 30ml anhydrous tetrahydrofuran, cool to -78°C, slowly add 6.5ml (15.6mmol) of 2.4M butyllithium solution dropwise, and keep warm for 30min. 4.82 g (14.2 mmol) of 4,4'-dibromobenzophenone was added. After 12 hours, deionized water and 3.7 g (14.2 mmol) of tetrabutylammonium fluoride were added. The organic layer was extracted with dichloromethane, spin-dried and passed through the column with dichloromethane:petroleum ether=3:1 to obtain a light yellow solid m=5.23g, η=98%;

[0050] The...

Embodiment 2

[0087] The synthetic method of photochromic polymer 2 containing spiro group, comprises the following steps:

[0088] Step 1. Using trimethylsilylacetylene as a raw material, under the condition of nitrogen protection at -78°C, through the reaction of butyl lithium and 4-bromobenzophenone in equal amounts to generate a hydroxyl-containing terminal alkyne bond compound;

[0089] The reaction formula is:

[0090]

[0091] The specific operation is: add 1.67g (17mmol) TMSA to a 250ml three-necked flask, add 2.4g (24mmol) TMSA to a 250ml three-necked flask, add 30ml anhydrous tetrahydrofuran, and cool to -78°C. Add 8.8ml (22mmol) of 2.4M butyllithium solution dropwise slowly, and keep warm for 30min. Add 5.22 g (20 mmol) of 4 dibromobenzophenone. After 12 hours, deionized water and 5.23 g (20 mmol) of tetrabutylammonium fluoride were added. The organic layer was extracted with dichloromethane, spin-dried and passed through the column with dichloromethane:petroleum ether=3:1 ...

Embodiment 3

[0128] The synthetic method of photochromic polymer 3 containing spiro group, comprises the following steps:

[0129] Step 1, the same as Step 1 in Example 2 to obtain a hydroxyl-containing terminal acetylenic bond compound.

[0130] Step 2, the product obtained in step 1 is dehydrated with 4,4'-biphenyldiphenol under the catalysis of pyridine p-toluenesulfonate with a mole fraction ratio of 5% through three times the equivalent of dehydrating agent trimethyl ortho acid ring-closing reaction to obtain a corresponding spiro-type photochromic unit;

[0131] The reaction formula is:

[0132]

[0133] The specific operation is: add 1.5g (5.2mmol) of bromide, 0.46g (2.5mmol) of 4,4'-biphenol, 0.07g (0.28mmol) of pyridine p-toluenesulfonate (PPTS) into the reaction tube, nitrogen Under atmosphere, 1.7 ml (15.6 mmol) of trimethyl orthoacid was added, and then 25 ml of 1,2-dichloroethane was added, and the mixture was stirred at 85° C. for 12 hours. Pass through the column with ...

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