Water-insoluble phosphonium salt bactericidal agent and its preparation method

Abstract

The invention relates to a water-insoluble quaternary ammonium salt bactericide and the preparation method thereof. The germicide is prepared by adopting silica gel inorganic material as a carrier and grafting amino-quaternary ammonium salt or quaternary ammonium-quaternary ammonium salt functional groups on the surface. The water-insoluble quaternary ammonium salt bactericide has excellent antibacterial activity, and has the advantages that the bactericide has a persistent effect of quaternary ammonium salt antibacterial polymer and also has a high-efficiency, quick and broad-spectrum antibacterial effect; the raw material is widely accessible; the cost is low; the synthetic process is simple. The bactericide is water-insoluble, and can be activated, regenerated and reutilized after the antibacterial rate is reduced, and is widely applicable to the sterilization of the fluid media such as various industrial and domestic waters, etc. and the preparation of antibacterial materials.

Description

technical field

[0001] The invention relates to a bactericide, more precisely a water-insoluble quaternary phosphonium salt bactericide with silica gel inorganic materials as carriers. The invention also relates to a preparation method of the water-insoluble quaternary phosphonium salt fungicide. Background technique

[0002] In order to overcome the shortcomings of water-soluble fungicides such as high toxicity, easy foaming, irritation, and residual toxicity after being discharged with sewage, people began to study water-insoluble fungicide polymers.

[0003] US 6,261,538 synthesized a class of water-insoluble polyquaternary phosphonium salt fungicides, which were prepared by using resins capable of chloromethylation as carriers, immobilized amino-quaternary phosphonium salts, quaternary ammonium-quaternary phosphonium salts and other fungicidal active components. . The above-mentioned bactericide has rapid and efficient bactericidal activity, can be used repeatedly, and...

Examples

Embodiment 1

[0047] Mix 21g (0.08mol) of triphenylphosphine, 20.2g (0.1mol) of 1,3-dibromopropane, add 100ml of xylene as a solvent, stir and heat to reflux at 100°C for 16h, the reaction is carried out under nitrogen protection, cooling, Filter, wash with 50ml of diethyl ether, and dry under vacuum below 100°C to obtain the crude product of 3-bromopropyltriphenyl quaternary phosphonium salt, and the reaction yield is about 90%. The reaction product was purified by recrystallization from ethanol and dried under vacuum at 100°C. The structural formula is Br(CH 2 ) 3 P + Ph 3 ·Br - .

Embodiment 2

[0049] Add about 15ml of KH550 (γ-aminopropyltriethoxysilane) into a 250ml three-necked flask, Na 2 CO 3 About 2.3g, absolute ethanol 40ml. 3-bromopropyl triphenyl quaternary phosphonium salt Br(CH 2 ) 3 P + Ph 3 ·Br - 10g was pre-dissolved in hot ethanol solution, added dropwise under stirring and reflux, dripping was completed in about 6 hours, and then refluxed and stirred for 4 hours. After the reaction was completed, the inorganic salt was filtered off while hot, the solvent was removed by rotary distillation, and a large amount of ether was added to the residue , a white solid was precipitated, filtered to obtain a white solid crude product. CH 2 Cl 2 Recrystallize and purify with diethyl ether, filter, wash twice with diethyl ether, and finally vacuum-dry to obtain quaternary phosphonium salt type amine propylated triethoxysilane, the structural formula is: (C 2 h 5 O) 3 Si(CH 2 ) 3 NH(CH 2 ) 3 P + Ph 3 ·Br - .

Embodiment 3

[0051] Take about 20g of 30-100 mesh coarse-porous microsphere silica gel, place it in 100ml of 5% methanesulfonic acid aqueous solution, stir and activate it at about 102°C for 4h, filter, wash with distilled water to make neutral, and put it under 100°C after suction filtration Vacuum dry.

[0052] Mix 1g of activated coarse-porous microsphere silica gel with 2.58g of quaternary phosphonium salt-type aminopropylated triethoxysilane prepared in Example 2, use ethanol and water as solvents, stir and heat to reflux for 24h, and react under nitrogen protection, the product Extract with ethanol for 6 hours, and dry under vacuum below 60°C to obtain a water-insoluble amino-quaternary phosphonium salt fungicide with silica gel as the carrier.

technical field

[0001] The invention relates to a bactericide, more precisely a water-insoluble quaternary phosphonium salt bactericide with silica gel inorganic materials as carriers. The invention also relates to a preparation method of the water-insoluble quaternary phosphonium salt fungicide. Background technique

[0002] In order to overcome the shortcomings of water-soluble fungicides such as high toxicity, easy foaming, irritation, and residual toxicity after being discharged with sewage, people began to study water-insoluble fungicide polymers.

[0003] US 6,261,538 synthesized a class of water-insoluble polyquaternary phosphonium salt fungicides, which were prepared by using resins capable of chloromethylation as carriers, immobilized amino-quaternary phosphonium salts, quaternary ammonium-quaternary phosphonium salts and other fungicidal active components. . The above-mentioned bactericide has rapid and efficient bactericidal activity, can be used repeatedly, and...

Examples

Embodiment 1

[0047] Mix 21g (0.08mol) of triphenylphosphine, 20.2g (0.1mol) of 1,3-dibromopropane, add 100ml of xylene as a solvent, stir and heat to reflux at 100°C for 16h, the reaction is carried out under nitrogen protection, cooling, Filter, wash with 50ml of diethyl ether, and dry under vacuum below 100°C to obtain the crude product of 3-bromopropyltriphenyl quaternary phosphonium salt, and the reaction yield is about 90%. The reaction product was purified by recrystallization from ethanol and dried under vacuum at 100°C. The structural formula is Br(CH 2 ) 3 P + Ph 3 ·Br - .

Embodiment 2

[0049] Add about 15ml of KH550 (γ-aminopropyltriethoxysilane) into a 250ml three-necked flask, Na 2 CO 3 About 2.3g, absolute ethanol 40ml. 3-bromopropyl triphenyl quaternary phosphonium salt Br(CH 2 ) 3 P + Ph 3 ·Br - 10g was pre-dissolved in hot ethanol solution, added dropwise under stirring and reflux, dripping was completed in about 6 hours, and then refluxed and stirred for 4 hours. After the reaction was completed, the inorganic salt was filtered off while hot, the solvent was removed by rotary distillation, and a large amount of ether was added to the residue , a white solid was precipitated, filtered to obtain a white solid crude product. CH 2 Cl 2 Recrystallize and purify with diethyl ether, filter, wash twice with diethyl ether, and finally vacuum-dry to obtain quaternary phosphonium salt type amine propylated triethoxysilane, the structural formula is: (C 2 h 5 O) 3 Si(CH 2 ) 3 NH(CH 2 ) 3 P + Ph 3 ·Br - .

Embodiment 3

[0051] Take about 20g of 30-100 mesh coarse-porous microsphere silica gel, place it in 100ml of 5% methanesulfonic acid aqueous solution, stir and activate it at about 102°C for 4h, filter, wash with distilled water to make neutral, and put it under 100°C after suction filtration Vacuum dry.

[0052] Mix 1g of activated coarse-porous microsphere silica gel with 2.58g of quaternary phosphonium salt-type aminopropylated triethoxysilane prepared in Example 2, use ethanol and water as solvents, stir and heat to reflux for 24h, and react under nitrogen protection, the product Extract with ethanol for 6 hours, and dry under vacuum below 60°C to obtain a water-insoluble amino-quaternary phosphonium salt fungicide with silica gel as the carrier.

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