CN104126870B - A kind of anionic polymer is modified the preparation method and applications of cellulose acetate - Google Patents

Abstract

The invention relates to a preparation method and application of anionic polymer modified cellulose acetate, belonging to the technical field of tobacco materials. Under the action of an initiator, the monomer with a sulfonic acid group or a carboxyl group and containing a monoethylenically unsaturated monomer is initiated and grafted onto the cellulose acetate. The filter tip prepared from the modified cellulose acetate of the present invention has obvious adsorption effect on smoke, especially remarkable selective adsorption effect on ammonia, nitrosamine and the like. Simultaneously, the process method used in the present invention is simple, the preparation cost is low, the flue gas adsorption effect is good, large-scale industrial production is possible, and the market application prospect is good.

Description

A kind of preparation method and application of anionic polymer modified cellulose acetate

technical field

The invention belongs to the technical field of tobacco materials, and in particular relates to a preparation method and application of anionic polymer modified cellulose acetate. The modified cellulose acetate can be used to prepare cigarette filter rods.

Background technique

There are more than 6,000 compounds in cigarette smoke, some of which have been identified as harmful, such as carbon monoxide, nitrogen oxides, aldehydes, phenols, free radicals, nitrosamines, and polycyclic aromatic hydrocarbons, which are considered to be carcinogenic or Substances that promote carcinogenicity. As a bridge between smokers and mainstream smoke, filters can effectively filter out some harmful components in smoke, so they have been widely valued and applied. At present, there are three types of conventional cigarette filter materials in the international market: paper filter, acetate filter and polypropylene fiber filter, among which acetate filter is the most widely used.

With the improvement of health awareness, people's requirements for cigarettes are getting higher and higher. While it is required to retain the flavor and flavor of cigarettes, it is also required to selectively reduce harmful components in smoke. Therefore, further increase the use of acetic acid for filters The selective adsorption and filtering effect of the fiber filter has become a bottleneck of cellulose acetate for cigarettes.

Contents of the invention

The object of the present invention is to provide a kind of preparation method and application of anionic polymer modified cellulose acetate cellulose with good stability, simple process, easy operation and wide application. The filter tip rod prepared by the modified cellulose acetate has obvious adsorption effect on smoke, especially has remarkable selective adsorption effect on ammonia, nitrosamine and the like.

According to the idea of molecular design, the present invention uses an initiator to graft the anionic polymer to cellulose acetate, and utilizes the acid-base interaction and hydrogen bond interaction between the anionic polymer and the harmful components of the smoke, thereby realizing the harmful effects of the smoke. Selective adsorption of components.

The technical scheme that the present invention adopts is as follows:

A kind of preparation method of anionic polymer modified cellulose acetate, concrete reaction is as follows: monomer solution is made into concentration and is 1-100g/L monomer solution in the solvent, then adds cellulose acetate, and cellulose acetate add-on and The volume ratio of the monomer solution is 0.1-100g/L, add the initiator at the same time, react under the protection of nitrogen, the reaction temperature is 50-100°C, and the reaction time is 0.5-24h. After the reaction is completed, the product is separated and purified to obtain the cation Polymer modified cellulose acetate; the volume ratio of initiator addition to monomer solution is 0.01g/L-10g/L;

The said monomer contains at least one monoethylenically unsaturated monomer, and the monomer has a sulfonic acid group or a carboxyl group.

The cellulose acetate described in the technical solution of the present invention is cellulose acetate or cellulose diacetate, that is, the hydroxyacetylation degree thereof is 0-2.8.

The monomer described in the technical solution of the present invention is acrylic acid, methacrylic acid, cinnamic acid, maleic acid, styrenesulfonic acid, vinylsulfonic acid or 2-acrylamide-2-methylpropanesulfonic acid.

In the technical solution of the present invention, it is further preferred that the initiator is azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, persulfuric acid Sodium, benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, potassium permanganate, ceric ammonium nitrate, potassium dichromate, or ferric chloride.

In the technical scheme of the present invention, it is further preferred that the described solvent is water, ethanol, methanol, benzene, toluene, xylene, methylene dichloride, ethylene dichloride, chloroform, n-hexane, cyclohexane, ether, Acetone, acetonitrile, tetrahydrofuran, pyridine, dimethylsulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

The application of the anionic polymer modified cellulose acetate prepared by the above preparation method as the preparation of cigarette filter rods.

Compared with the prior art, the present invention has the beneficial effects as follows: (1) The process method used in the present invention is simple, the preparation cost is low, the flue gas adsorption effect is good, it can be produced in a large scale, and has a good market application prospect; (2) ) The modified cellulose acetate obtained by the present invention can be applied to the industrial production of filter rods with good selective interception of harmful components in smoke, and the prepared filter rods have obvious adsorption effect on smoke, especially for ammonia, nitrosamines It has a remarkable selective adsorption effect; (3) the present invention grafts active functional groups on cellulose acetate and utilizes the special interaction between the functional groups and the harmful components of the smoke to achieve selective adsorption of the harmful components of the smoke. At the same time, the present invention can obtain different functionalized modified cellulose acetates by changing the reaction conditions and selecting different graft polymers.

detailed description

The present invention will be further described in detail below in conjunction with the examples.

Example 1

Add 0.1g cellulose diacetate and 0.01g azobisisobutylcyanide to 1L of 1g/L acrylic acid in water reaction solution, under the condition of nitrogen protection, react at 50°C for 0.5h, after repeated washing with water and ethanol , and dried in vacuum to obtain a modified cellulose acetate with a grafting rate of 16%. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 5%, the ammonia by 10%, and the nitrosamine by 9%.

Example 2

Add 100g of cellulose diacetate and 10g of azobisisobutylcyanide to 1L of 10g/L methacrylic acid in N, N-dimethylformamide reaction solution, and react at 100°C for 12h under nitrogen protection. , washed repeatedly with water and ethanol, and then dried in vacuum to obtain a modified cellulose acetate with a grafting rate of 32%. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 12%, the ammonia by 11%, and the nitrosamine by 15%.

Example 3

Add 10g of cellulose acetate and 1g of sodium persulfate to 1L of 100g/L cinnamic acid ethanol reaction solution, under the condition of nitrogen protection, react at 85°C for 24h, wash with water and ethanol repeatedly, and vacuum dry, that is A modified cellulose acetate with a graft rate of 21% was obtained. The obtained modified cellulose acetate is added to the filter tip, and the smoke test of the final cigarette product can reduce tar by 15%, ammonia by 20%, and nitrosamine by 22%.

Example 4

Add 50g of cellulose acetate and 1g of potassium permanganate to 1L of 100g/L maleic acid dimethyl sulfoxide reaction solution, under the condition of nitrogen protection, react at 55°C for 12h, wash with water and ethanol repeatedly Afterwards, vacuum-dried to obtain a modified cellulose acetate with a grafting rate of 13%. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 13%, the ammonia by 15%, and the nitrosamine by 17%.

Example 5

Add 10g cellulose diacetate and 3g cerium ammonium nitrate to 1L reaction solution of 60g/L p-styrene sulfonic acid in acetone, under the condition of nitrogen protection, react at 65°C for 24h, wash with water and ethanol repeatedly, vacuum After drying, a modified cellulose acetate with a graft rate of 16% was obtained. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce tar by 21%, ammonia by 13%, and nitrosamine by 22%.

Example 6

Add 20g of cellulose diacetate and 2g of sodium persulfate to 1L of a reaction solution of 100g/L vinylsulfonic acid in chloroform, and react at 80°C for 18h under nitrogen protection. After repeated washing with water and ethanol, After vacuum drying, the modified cellulose acetate with a graft rate of 28% was obtained. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 11%, the ammonia by 14%, and the nitrosamine by 18%.

Example 7

Add 60g of cellulose acetate and 7g of dimethyl azobisisobutyrate to 1L of 20g/L 2-acrylamide-2-methylpropanesulfonic acid-benzene reaction solution, under the condition of nitrogen protection, at 60°C The reaction was carried out for 24 hours, washed repeatedly with water and ethanol, and dried in vacuum to obtain a modified cellulose acetate with a grafting rate of 26%. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 8%, the ammonia by 16%, and the nitrosamine by 13%.

Example 8

Add 50g of cellulose acetate and 3g of hydrogen peroxide to 1L of 30g/L methacrylic acid-toluene reaction solution, under the condition of nitrogen protection, react at 85°C for 12h, wash with water and ethanol repeatedly, and vacuum dry. That is, a modified cellulose acetate with a graft rate of 23% was obtained. The obtained modified cellulose acetate is added to the filter tip, and the smoke test of the final cigarette product can reduce tar by 13%, ammonia by 16%, and nitrosamine by 15%.

Example 9

Add 40g cellulose diacetate and 3g ammonium persulfate to 1L reaction solution of 50g/L 2-acrylamide-2-methylpropanesulfonic acid in xylene, react at 75°C for 4h under nitrogen protection, and water After repeated washing with ethanol, vacuum drying was performed to obtain a modified cellulose acetate with a grafting rate of 33%. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce tar by 11%, ammonia by 12%, and nitrosamine by 18%.

Example 10

Add 60g of cellulose acetate and 4g of benzoyl peroxide to 1L of 70g/L cinnamic acid in dichloromethane reaction solution, under the condition of nitrogen protection, react at 55°C for 3h, after repeated washing with water and ethanol, After vacuum drying, the modified cellulose acetate with a graft rate of 28% was obtained. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce tar by 18%, ammonia by 16%, and nitrosamine by 19%.

Example 11

Add 70g of cellulose acetate and 10g of benzoyl tert-butyl peroxide to 1L of 60g/L 2-acrylamide-2-methylpropanesulfonic acid in n-hexane reaction solution, under the condition of nitrogen protection, at 65°C The reaction was carried out for 8 hours, washed repeatedly with water and ethanol, and dried in vacuum to obtain a modified cellulose acetate with a grafting rate of 36%. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 13%, the ammonia by 15%, and the nitrosamine by 20%.

Example 12

Add 80g cellulose diacetate and 5g potassium dichromate to 1L reaction solution of 100g/L styrenesulfonic acid in cyclohexane, react at 90°C for 5h under nitrogen protection, and wash with water and ethanol repeatedly , and dried in vacuum to obtain a modified cellulose acetate with a graft rate of 24%. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce tar by 18%, ammonia by 14%, and nitrosamine by 14%.

Example 13

Add 30g of cellulose diacetate and 6g of ferric chloride to 1L of the reaction solution of 80g/L vinylsulfonic acid ether, under the condition of nitrogen protection, react at 80°C for 18h, wash with water and ethanol repeatedly, and dry in vacuum , That is, a modified cellulose acetate with a grafting rate of 19% was obtained. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 10%, the ammonia by 12%, and the nitrosamine by 16%.

Example 14

Add 40g cellulose acetate and 9g azobisisoheptanonitrile to 1L reaction solution of 90g/L acrylic acid in acetonitrile, react at 60°C for 12h under nitrogen protection, wash with water and ethanol repeatedly, then vacuum dry , That is, a modified cellulose acetate with a grafting rate of 33% was obtained. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 13%, the ammonia by 14%, and the nitrosamine by 12%.

Example 15

Add 80g of cellulose diacetate and 5g of methyl ethyl ketone peroxide to 1L of 100g/L maleic acid-pyridine reaction solution, under the condition of nitrogen protection, react at 50°C for 24h, wash with water and ethanol repeatedly, and vacuum dry. That is, a modified cellulose acetate with a graft rate of 20% was obtained. The obtained modified cellulose acetate is added to the filter tip, and the final cigarette product, after the smoke test, can reduce the tar by 13%, the ammonia by 15%, and the nitrosamine by 21%.

Claims (2)

1. a kind of anionic polymer is modified the preparation method of cellulose acetate, it is characterised in that specific reaction is as follows：By monomer To be made into concentration in a solvent be 1-100g/L monomer solutions for dissolving, then adds cellulose acetate, cellulose acetate addition and The volume ratio of monomer solution is 0.1-100g/L, while adds initiator, is reacted under nitrogen protection, reaction temperature 50-100 DEG C, reaction time 0.5-24h, by product separating-purifying after the completion of reaction, that is, obtain anionic polymer and be modified acetate fiber Element；Initiator addition and monomer solution volume ratio 0.01g/L-10g/L；

Described monomer is at least to contain a kind of undersaturated monomer of mono-vinyl, and the monomer carries sulfonic group or carboxyl；Institute The monomer stated is cinnamic acid, styrene sulfonic acid or vinyl sulfonic acid；

Described cellulose acetate is cellulose diacetate；

Described initiator is azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl, hydrogen peroxide, over cure Sour ammonium, sodium peroxydisulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, potassium permanganate, ammonium ceric nitrate, Potassium bichromate or iron chloride；

Described solvent be water, ethanol, methanol, benzene,toluene,xylene, dichloromethane, dichloroethanes, chloroform, just oneself Alkane, hexamethylene, ether, acetone, acetonitrile, tetrahydrofuran, pyridine, dimethyl sulfoxide (DMSO), DMF or N, N- bis- Methylacetamide.

2. the anionic polymer prepared by claim 1 is modified cellulose acetate as the application for preparing cigarette filter stick.