CN111387545B - Preparation method of novel filter stick capable of reducing release amount of crotonaldehyde in smoke - Google Patents

Abstract

The invention relates to a preparation method of a novel filter rod that can reduce the release amount of crotonaldehyde in flue gas. After high internal phase emulsion polymerization is carried out in a specific filter rod mold, it is reacted with an amination reagent to prepare a filter rod that can reduce the amount of crotonaldehyde in flue gas. New filter rod for crotonaldehyde release. The new filter rod can be directly formed into a filter rod with a specific circumference and length in the filter rod forming mold, and has a certain strength, which can meet the requirements of tipping cigarettes; the filter rod has large pores of micron size, and the pores are They are interoperable and can transmit cigarette smoke; after the reaction between epoxy groups and amination reagents, the filter rods have amine functional groups, which can reduce the release of crotonaldehyde in the smoke; the use of silica nanoparticles The particle is used as particle emulsifier to increase the strength of the filter rod; the particle emulsifier is modified with a modifier, which has a polymerizable double bond, which is conducive to high internal phase emulsion polymerization; the method of radiation polymerization is used, no chemical initiator is added, and It has the effect of disinfection and sterilization.

Description

A kind of preparation method of novel filter rod that can reduce the release amount of crotonaldehyde in flue gas

technical field

The invention belongs to the technical field of filter rod preparation, in particular to a preparation method of a novel filter rod which can reduce the release amount of crotonaldehyde in flue gas.

Background technique

Crotonaldehyde is one of the main harmful components in mainstream cigarette smoke. The "Research on Cigarette Hazard Indicator System" project has studied the relationship between the release of harmful components and the biological activity of smoke, and found that crotonaldehyde is the most important factor affecting the harmfulness of mainstream cigarette smoke. Therefore, reducing the crotonaldehyde content in cigarette smoke is of great significance for reducing the harm of cigarettes.

There have also been many related studies at home and abroad on how to reduce crotonaldehyde in cigarette smoke. Patent CN104941606B discloses an adsorbent for reducing the release of crotonaldehyde in mainstream cigarette smoke, the adsorbent belongs to a molecular sieve-polyethersulfone composite material. Patent CN107286275B discloses an amino resin that selectively reduces the release of HCN and crotonaldehyde in cigarette smoke. The amino resin is a polymethyl methacrylate resin ball with amino groups grafted on the surface. Feng Shouai et al. (Feng Shouai, Huang Taisong, Zou Kexing, etc.. Hydrophobic nano-SiO2 selectively reduces the content of harmful components in cigarette smoke [J]. Tobacco Science and Technology, 2011(10): 49-53.) prepared hydrophobic nano-silica, And it was added to cut tobacco and filter to study its harm reduction effect. Studies have shown that adding to cut tobacco can reduce the release of phenol by 27.2% and the release of crotonaldehyde by 12.4%. Patents CN102178351A, CN102119786A and CN102178350A respectively disclose that adding soybean fibrin granules, soybean glutinous rice grains and silk fibroin to the filter tip can reduce the release of crotonaldehyde in the smoke by 16.2-33.8%, and at the same time reduce the amount of crotonaldehyde in the smoke by 16.2-33.8%. The harmful substances are also reduced in different ways, making the smoke have a distinct sweetness, reducing the irritation of the smoke, and increasing the richness and delicacy of the cigarette flavor. Patent CN106858709B discloses a preparation method of an amino acid ionic liquid that selectively reduces crotonaldehyde in mainstream cigarette smoke. The acid-base neutralization reaction occurs between the carboxyl group of amino acid and the hydroxide group of tetraalkylammonium hydroxide to synthesize tetraalkylene. Ammonium hydroxide type amino acid ionic liquid. Patent CN102942654A discloses a preparation method of an adsorbent that can effectively reduce the content of crotonaldehyde in cigarette smoke, using n-butyraldehyde as a false template, and using methacrylic acid, acrylamide, 2-vinylpyridine or 4-vinylpyridine as The functional monomer is prepared by precipitation polymerization with methanol as pore-forming solvent and ethylene glycol dimethacrylate as cross-linking agent.

At present, cigarettes generally use diacetate tow filter rods and polypropylene tow filter rods as filter tips. These two filter rods are made by first preparing diacetate fiber tow and polypropylene tow, and then forming them into conventional filter rods by filter rod forming equipment. Filter rods for cigarettes (generally 7.7mm in diameter), filter rods for medium cigarettes (generally 7.0mm or 6.0mm in diameter) or filter rods for thin cigarettes (5.4mm in diameter). However, this kind of filter rod needs to prepare the tow first, and then form it into a filter rod, and the steps are relatively complicated.

The polymer interconnected porous material (PolyHIPE) is a high internal phase emulsion (HIPE, also known as ultra-concentrated emulsion, the volume fraction of the dispersed phase is more than 74%, and the droplets are squeezed with each other and become a surface active substance. It is a polyhedral-shaped vacuole isolated by the continuous phase film of the agent, and an interconnected porous material obtained by polymerizing the monomer of the continuous phase. The polymer interconnected porous material usually contains three kinds of pores: (1) The pores formed by the dispersed phase template are called It is called "void", and the pore size is in the micron scale; (2) the hole formed between two adjacent cells is called "window", and the pore size is in the micron scale, which plays the role of interconnecting cells. (3) The pores formed on the cell wall by adding a pore-forming agent to the continuous phase monomer are called "pores", and the pore size is in the nanometer scale. The surface area is greatly increased.

The polymer intercommunicating porous material has a good potential to become a new type of filter rod, which is embodied in: (1) It can be directly formed into a filter rod of the target circumference and length in the filter rod preparation mold, and has a certain strength to meet the requirements of cigarette tipping. (2) The material has micron-scale macropores, and the pores are interconnected, which is conducive to the transmission of flue gas; (3) After the epoxy group is reacted with the amination reagent, the filter is filtered. The rod has an amine functional group, which can reduce the release of crotonaldehyde in the flue gas; (4) the use of silica nanoparticles as a particle emulsifier can increase the strength of the filter rod; (5) the particle emulsifier is modified by a modifier , the modifier has a polymerizable double bond, which is conducive to high internal phase emulsion polymerization; (6) the method of radiation polymerization is used, no chemical initiator is added, and it has the effect of disinfection and sterilization.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a method for preparing a novel filter rod that can reduce the amount of crotonaldehyde released in the flue gas, so as to solve the need to prepare acetate tow first for the commonly used acetate tow filter rods and polypropylene tow filter rods And polypropylene tow, and then through the filter rod forming equipment to form the problem of the complex preparation process of the filter rod.

The present invention is achieved through the following technical solutions:

A preparation method of a novel filter rod that can reduce the amount of crotonaldehyde released in flue gas, the specific steps are as follows:

1) Configure an oil phase, the composition of the oil phase is: 2-8ml of glycidyl methacrylate, 0-3ml of methyl methacrylate, 0-3ml of 2-ethylhexyl acrylate, 0.5-5ml cross-linking agent and 1-10g particle emulsifier;

2) configure a water phase, the composition of the water phase is: 40-90ml of water and 0.1-1.5g of inorganic salt;

3) at 500～700rpm, slowly add the water phase to the oil phase to form a high internal phase emulsion, transfer the high internal phase emulsion to a filter rod mold, and seal after 10～20min of nitrogen gas;

4) Put the filter rod mold equipped with the high internal phase emulsion in step 3) into a 1.3×10 ¹⁵ Bq ⁶⁰ Co source, the dose rate is 20-80 Gy/min, and the irradiation time is 24-48 h;

5) Add excess amination reagent to the filter rod-shaped solid product obtained in step 4) and react for 24 to 48 hours, and the reaction temperature is 40 to 60 °C;

6) The product of step 5) is extracted with water and ethanol for 24 hours, and dried in a vacuum oven to obtain a novel filter rod that can reduce the amount of crotonaldehyde released in the flue gas.

The crosslinking agent is one or more combinations of ethylene glycol bismethacrylate, trimethylolpropane trimethacrylate or glycerol tris(α-methacrylate).

The particle emulsifier is a silica nanoparticle whose surface is modified by a modifier.

The modifier is a polymerizable modifier prepared by opening the double bond in oleic acid to generate a dihydroxy group, and then performing an esterification reaction with acrylic acid.

The inorganic salt is one of calcium chloride, sodium chloride or magnesium sulfate.

The amination reagent is ethylenediamine or propylenediamine.

The beneficial effects of the present invention are:

(1) In the filter rod preparation mold, it can be directly formed into a filter rod with a target circumference and length, and has a certain strength to meet the requirements of cigarette tipping, and the preparation steps are simple;

(2) The material has micron-scale macropores, and the pores are interconnected, which is conducive to the transmission of flue gas;

(3) After the epoxy group is reacted with the amination reagent, the filter rod has an amino functional group, which can reduce the amount of crotonaldehyde released in the flue gas;

(4) The strength of the filter rod can be increased by using silica particles as the particle emulsifier;

(5) The particle emulsifier is modified with a modifier, and the modifier has a polymerizable double bond, which is conducive to high internal phase emulsion polymerization;

(6) The method of radiation polymerization is adopted, no chemical initiator is added, and it has the effect of disinfection and sterilization.

Detailed ways

The technical solutions of the present invention will be described in detail by the following examples. The following examples are only exemplary, and can only be used to explain and illustrate the technical solutions of the present invention, but cannot be construed as limitations on the technical solutions of the present invention.

In this application, the particle emulsifier is a silica nanoparticle whose surface is modified with a modifier, wherein the modifier is a polymerizable polymer prepared by opening the double bond in oleic acid to generate dihydroxyl, and then performing an esterification reaction with acrylic acid. Modifier, the specific reaction equation is as follows:

Example 1

The oil phase is prepared first, and the composition of the oil phase is 8 ml of glycidyl methacrylate, 2 ml of methyl methacrylate, 0.5 ml of ethylene glycol bismethacrylate, and 5 g of modified silica nanoparticles.

An aqueous phase was prepared, and 64 ml of water and 0.5 g of calcium chloride were uniformly mixed to prepare an aqueous phase.

Under high-speed stirring at 500 rpm, the water phase was slowly added to the oil phase to form a high internal phase emulsion, which was poured into a filter rod forming mold with a diameter of 7.7 mm and a length of 100 mm, and sealed with nitrogen for 10 minutes.

In the technical solution of the present application, the forming mold of the filter rod can be changed as required, such as a filter rod mold with a diameter of 7.0mm or 6.0mm or 5.4mm and a length of 100mm or 120mm or 144mm, or other types of molds. , the model of the filter rod mold does not affect the realization of the technical solution of the application, which is the case in the following embodiments of the application or other situations where your filter rod mold is implemented.

Subsequently, the mold with the high internal coating emulsion was placed in a 1.3×10 ¹⁵ Bq ⁶⁰ Co source, the dose rate was 36 Gy/min, and the irradiation time was 24 h. The obtained solid product was placed in excess ethylenediamine solution at 40°C for reaction for 24 hours, extracted with water and ethanol for 24 hours, and dried in a vacuum oven to obtain the final filter rod. The obtained filter rod tipped cigarette, compared with the unplugged cigarette, the reduction rate of crotonaldehyde release in mainstream smoke reached 30.5%.

Example 2

First configure the oil phase. The composition of the oil phase is 4ml of glycidyl methacrylate, 0.5ml of 2-ethylhexyl acrylate, 3ml of trimethylolpropane trimethacrylate, and 3g of modified silica nanoparticles. particle.

An aqueous phase was prepared, and 60 ml of water and 0.5 g of sodium chloride were uniformly mixed to prepare an aqueous phase.

Under high-speed stirring at 500 rpm, the water phase was slowly added to the oil phase to form a high internal phase emulsion, which was poured into a filter rod forming mold with a diameter of 7.0 mm and a length of 120 mm, and sealed with nitrogen for 10 minutes. Then, the mold with the high internal phase emulsion was put into a 1.3×10 ¹⁵ Bq ⁶⁰ Co source, the dose rate was 36 Gy/min, and the irradiation time was 36 h.

The obtained solid product was placed in excess propylene diamine solution for 24 hours at 40°C, extracted with water and ethanol for 24 hours, and dried in a vacuum oven to obtain the final filter rod.

Example 3

The oil phase is prepared first, and the composition of the oil phase is 5 ml of glycidyl methacrylate, 2 ml of methyl methacrylate, 1 ml of glycerol tris(α-methacrylate), and 4 g of modified silica nanoparticles.

An aqueous phase was prepared, and 70 ml of water and 1.5 g of magnesium sulfate were mixed uniformly to prepare an aqueous phase.

Under high-speed stirring at 700 rpm, the water phase was slowly added to the oil phase to form a high internal phase emulsion, which was poured into a filter rod forming mold with a diameter of 6.0 mm and a length of 120 mm, and sealed with nitrogen for 10 minutes.

Then the mold with the high internal emulsion was put into a 1.3×10 ¹⁵ Bq ⁶⁰ Co source, the dose rate was 36 Gy/min, and the irradiation time was 36 h.

The obtained solid product was placed in excess ethylenediamine solution at 50°C for reaction for 24 hours, extracted with water and ethanol for 24 hours, and dried in a vacuum oven to obtain the final filter rod.

Example 4

The oil phase is prepared first, and the composition of the oil phase is 6 ml of glycidyl methacrylate, 2 ml of methyl methacrylate, 1 ml of glycerol tris(αˉ methacrylate), and 4 g of modified silica nanoparticles.

An aqueous phase was prepared, and 70 ml of water and 1.5 g of magnesium sulfate were uniformly mixed to prepare an aqueous phase.

Under high-speed stirring at 700 rpm, the water phase was slowly added to the oil phase to form a high internal phase emulsion, which was poured into a filter rod forming mold with a diameter of 5.4 mm and a length of 120 mm, and sealed with nitrogen for 10 minutes.

Then, the mold with the high internal phase emulsion was put into a 1.3×10 ¹⁵ Bq ⁶⁰ Co source, the dose rate was 36 Gy/min, and the irradiation time was 48 h.

The obtained solid product was placed in excess ethylenediamine solution at 50°C for reaction for 24 hours, extracted with water and ethanol for 24 hours, and dried in a vacuum oven to obtain the final filter rod.

Example 5

The oil phase is prepared first, and the composition of the oil phase is 6 ml of glycidyl methacrylate, 2 ml of methyl methacrylate, 0.5 ml of ethylene glycol bismethacrylate, and 4 g of modified silica nanoparticles.

Then, the water phase is prepared, and 64 ml of water and 0.5 g of calcium chloride are uniformly mixed to prepare the water phase.

Under high-speed stirring at 500 rpm, the water phase was slowly added to the oil phase to form a high internal phase emulsion, which was poured into a filter rod forming mold with a diameter of 7.7 mm and a length of 144 mm, and sealed with nitrogen for 10 minutes.

Then, the mold with the high internal phase emulsion was put into a 1.3×10 ¹⁵ Bq ⁶⁰ Co source, the dose rate was 36 Gy/min, and the irradiation time was 24 h.

The obtained solid product was placed in excess ethylenediamine solution at 50°C for reaction for 24 hours, extracted with water and ethanol for 24 hours, and dried in a vacuum oven to obtain the final filter rod.

The novel filter rods prepared by Examples 1 to 5 can be directly formed into filter rods with a specific circumference and length in a filter rod forming mold, and have a certain strength, which can meet the requirements of tipping cigarettes; among the prepared novel filter rods It has large pores of micron size, and the pores are interconnected, which can make cigarette smoke transport; after the reaction between epoxy groups and amination reagents, the filter rods have amine functional groups, which can reduce smoke The amount of crotonaldehyde released; the use of silica nanoparticles as particle emulsifier can increase the strength of the filter rod; the particle emulsifier is modified with a modifier, which has a polymerizable double bond, which is conducive to high internal phase emulsion polymerization; using radiation The polymerization method does not add chemical initiators, and has the effect of disinfection and sterilization.

The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited to this. Any changes or replacements that are not thought of without creative work should be covered within the protection scope of the present invention. Therefore, the present invention The scope of protection shall be subject to the scope of protection defined by the claims.

Claims (4)

1. A preparation method of a novel filter stick capable of reducing the release amount of crotonaldehyde in smoke is characterized by comprising the following specific steps:

1) preparing an oil phase, wherein the oil phase comprises the following components: 2-8 ml of glycidyl methacrylate, 0-3 ml of methyl methacrylate, 0-3 ml of 2-ethylhexyl acrylate, 0.5-5 ml of a cross-linking agent and 1-10 g of a particle emulsifier;

2) preparing an aqueous phase, wherein the composition of the aqueous phase is as follows: 40-90 ml of water and 0.1-1.5 g of inorganic salt;

3) slowly adding the water phase into the oil phase at 500-700 rpm to form a high internal phase emulsion, transferring the high internal phase emulsion into a filter stick mold, introducing nitrogen for 10-20 min, and sealing;

4) putting the filter stick mould filled with the high internal phase emulsion in the step 3) into a mould of 1.3 multiplied by 10¹⁵ Bq ⁶⁰In a Co source, the dosage rate is 20-80 Gy/min, and the irradiation time is 24-48 h;

5) adding excessive amination reagent into the filter stick-shaped solid product obtained in the step 4), and reacting for 24-48 hours at the temperature of 40-60 ℃;

6) extracting the product obtained in the step 5) with water and ethanol for 24 hours respectively, and drying in a vacuum oven to obtain a novel filter stick capable of reducing the release amount of crotonaldehyde in smoke;

the particle emulsifier is silicon dioxide nano particles with the surfaces modified by a modifier;

the modifier is a polymerizable modifier prepared by opening double bonds in oleic acid to generate dihydroxy and then carrying out esterification reaction with acrylic acid.

2. The method for preparing a novel filter stick capable of reducing the release amount of crotonaldehyde in smoke according to claim 1, wherein the crosslinking agent is at least one of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or glycerol tri (alpha-methacrylate).

3. The method for preparing the novel filter stick capable of reducing the release amount of crotonaldehyde in smoke according to claim 1, wherein the inorganic salt is one of calcium chloride, sodium chloride or magnesium sulfate.

4. The method for preparing a novel filter stick capable of reducing the release amount of crotonaldehyde in smoke according to claim 1, wherein the amination reagent is ethylenediamine or propylenediamine.