CN104126870A - Manufacturing method and application of anionic polymer modified cellulose acetate - Google Patents
Manufacturing method and application of anionic polymer modified cellulose acetate Download PDFInfo
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- CN104126870A CN104126870A CN201410343628.1A CN201410343628A CN104126870A CN 104126870 A CN104126870 A CN 104126870A CN 201410343628 A CN201410343628 A CN 201410343628A CN 104126870 A CN104126870 A CN 104126870A
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- cellulose acetate
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Abstract
The invention relates to a manufacturing method and application of anionic polymer modified cellulose acetate, and belongs to the technical field of cigarette materials. Under the action of initiators, unsaturated monomers which are provided with sulfo groups or carboxyl and include single vinyl are triggered and grafted to the cellulose acetate. A filter tip manufactured through the modified cellulose acetate is obvious in smoke absorption effect, and the obvious selective absorption effect is especially achieved for ammonia, nitrosamine and the like. Meanwhile, the process method is simple and low in manufacturing cost, the smoke absorption effect is good, large-scale industrial production can be achieved, and the good market application prospect is achieved.
Description
Technical field
The invention belongs to smoking material technical field, be specifically related to a kind of preparation method and application of anionic polymer modification cellulose acetate, this modification cellulose acetate can be for the preparation of cigarette filter stick.
Background technology
In cigarette smoke, have more than 6000 to plant compound, wherein existing part is identified is harmful to, and as carbon monoxide, oxynitrides, aldehydes, phenols, free radical, nitrosamine and polycyclic aromatic hydrocarbon etc., be considered to may be carcinogenic or promote carcinogenic material.Filter tip is as the bridge between smoker and main flume, part harmful components in filtering flue gas effectively, thereby obtained paying attention to widely and application.At present, on international market, conventional cigarette has paper filter tip, acetate fiber filter tip and polypropylene fibre filter tip three types with filter material, and what be wherein most widely used is acetate fiber filter tip.
Raising along with health perception, people are more and more higher for the requirement of cigarette, when requiring to retain the very popular taste of wind of cigarette, requirement can optionally reduce the harmful components in flue gas again, therefore, further improve the selective absorption filter effect of acetate fiber filter tip for filter tip, become a bottleneck of cellulose acetate for cigarette.
Summary of the invention
The object of the present invention is to provide a kind of good stability, technique is simple, easy and simple to handle, preparation method and the application thereof of widely applicable anionic polymer modification cellulose acetate fibre element.The filter stick that this modification cellulose acetate prepares, obvious to flue gas adsorption effect, particularly ammonia, nitrosamine etc. is had to significant selective absorption effect.
The present invention, according to the thinking of MOLECULE DESIGN, utilizes initator, and by anionic polymer, modify and graft, to cellulose acetate, utilizes acid-base function and the hydrogen bond action of anionic polymer and harmful ingredients in flue gas, thereby realizes the selective absorption of harmful ingredients in flue gas.
The technical solution used in the present invention is as follows:
A kind of preparation method of anionic polymer modification cellulose acetate, concrete reaction is as follows: monomer is dissolved in in solvent, to be made into concentration be 1-100g/L monomer solution, then add cellulose acetate, the volume ratio of cellulose acetate addition and monomer solution is 0.1-100g/L, adds initator simultaneously, under nitrogen protection, reacts, reaction temperature is 50-100 ℃, reaction time is 0.5-24h, after having reacted, product separation is purified, and obtains cationic polymer modification cellulose acetate; Initator addition and monomer solution volume ratio 0.01g/L-10g/L;
Described monomer is at least containing the undersaturated monomer of a kind of mono-vinyl, and this monomer is with sulfonic group or carboxyl.
Cellulose acetate described in technical solution of the present invention is a cellulose acetate or cellulose diacetate, and its hydroxyl degree of acetylation is 0-2.8.
Described monomer described in technical solution of the present invention is acrylic acid, methacrylic acid, cinnamic acid, maleic acid, styrene sulfonic acid, vinyl sulfonic acid or 2-acrylamide-2-methyl propane sulfonic.
In technical solution of the present invention, further preferably described initator is azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl, hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, potassium permanganate, ammonium ceric nitrate, potassium bichromate or iron chloride.
In technical solution of the present invention, further preferably described solvent is water, ethanol, methyl alcohol, benzene,toluene,xylene, carrene, dichloroethanes, chloroform, n-hexane, cyclohexane, ether, acetone, acetonitrile, oxolane, pyridine, dimethyl sulfoxide (DMSO), N, dinethylformamide or DMA.
Anionic polymer modification cellulose acetate prepared by above-mentioned preparation method is as the application of preparing cigarette filter stick.
compared with prior art, its beneficial effect is in the present invention:(1) the present invention uses process is simple, preparation cost is low, and flue gas advantages of good adsorption effect can large-scale industrial production, has good market application foreground; (2) cellulose acetate that modification of the present invention obtains can be applied with suitability for industrialized production has the filter stick that good selectivity is held back harmful substances in flue gas, the filter stick preparing is obvious to flue gas adsorption effect, particularly ammonia, nitrosamine etc. is had to significant selective absorption effect; (3) the present invention is by grafting active function groups on cellulose acetate, utilize the special role between functional group and harmful ingredients in flue gas, can realize harmful ingredients in flue gas selective absorption flue gas is adsorbed, simultaneously, the present invention can, by changing reaction condition, select different graft polymers can obtain the cellulose acetate of the modification of difference in functionality.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
0.1g cellulose diacetate and 0.01g azo-bis-isobutyl cyanide are joined in the reaction solution of the acrylic acid water of 1g/L of 1L; under the condition of nitrogen protection, react 0.5h at 50 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 16% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 5%, and ammonia can reduce by 10%, and nitrosamine can reduce by 9%.
Embodiment 2
100g cellulose diacetate and 10g azo-bis-isobutyl cyanide are joined to the N of the 10g/L methacrylic acid of 1L; in the reaction solution of dinethylformamide; under the condition of nitrogen protection; at 100 ℃, react 12h; after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 32% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 12%, and ammonia can reduce by 11%, and nitrosamine can reduce by 15%.
Embodiment 3
10g mono-cellulose acetate and 1g sodium peroxydisulfate are joined in the reaction solution of ethanol of 100g/L cinnamic acid of 1L; under the condition of nitrogen protection, react 24h at 85 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 21% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 15%, and ammonia can reduce by 20%, and nitrosamine can reduce by 22%.
Embodiment 4
50g mono-cellulose acetate and 1g potassium permanganate are joined in the reaction solution of dimethyl sulfoxide (DMSO) of 100g/L maleic acid of 1L; under the condition of nitrogen protection, react 12h at 55 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 13% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 13%, and ammonia can reduce by 15%, and nitrosamine can reduce by 17%.
Embodiment 5
10g cellulose diacetate and 3g ammonium ceric nitrate are joined in the reaction solution of acetone of 60g/L p styrene sulfonic acid of 1L; under the condition of nitrogen protection, react 24h at 65 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 16% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 21%, and ammonia can reduce by 13%, and nitrosamine can reduce by 22%.
Embodiment 6
20g cellulose diacetate and 2g sodium peroxydisulfate are joined in the reaction solution of chloroform of 100g/L vinyl sulfonic acid of 1L; under the condition of nitrogen protection, react 18h at 80 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 28% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 11%, and ammonia can reduce by 14%, and nitrosamine can reduce by 18%.
Embodiment 7
60g mono-cellulose acetate and 7g azo-bis-iso-dimethyl are joined in the reaction solution of benzene of 20g/L2-acrylamide-2-methyl propane sulfonic of 1L; under the condition of nitrogen protection; at 60 ℃, react 24h; after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 26% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 8%, and ammonia can reduce by 16%, and nitrosamine can reduce by 13%.
Embodiment 8
50g mono-cellulose acetate and 3g hydrogen peroxide are joined in the reaction solution of toluene of 30g/L methacrylic acid of 1L; under the condition of nitrogen protection, react 12h at 85 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 23% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 13%, and ammonia can reduce by 16%, and nitrosamine can reduce by 15%.
Embodiment 9
40g cellulose diacetate and 3g ammonium persulfate are joined in the reaction solution of dimethylbenzene of 50g/L2-acrylamide-2-methyl propane sulfonic of 1L; under the condition of nitrogen protection, react 4h at 75 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 33% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 11%, and ammonia can reduce by 12%, and nitrosamine can reduce by 18%.
Embodiment 10
60g mono-cellulose acetate and 4g benzoyl peroxide are joined in the reaction solution of carrene of 70g/L cinnamic acid of 1L; under the condition of nitrogen protection, react 3h at 55 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 28% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 18%, and ammonia can reduce by 16%, and nitrosamine can reduce by 19%.
Embodiment 11
70g mono-cellulose acetate and the 10g benzoyl peroxide tert-butyl ester are joined in the reaction solution of n-hexane of 60g/L2-acrylamide-2-methyl propane sulfonic of 1L; under the condition of nitrogen protection; at 65 ℃, react 8h; after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 36% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 13%, and ammonia can reduce by 15%, and nitrosamine can reduce by 20%.
Embodiment 12
80g cellulose diacetate and 5g potassium bichromate are joined in the reaction solution of cyclohexane of 100g/L styrene sulfonic acid of 1L; under the condition of nitrogen protection, react 5h at 90 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 24% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 18%, and ammonia can reduce by 14%, and nitrosamine can reduce by 14%.
Embodiment 13
30g cellulose diacetate and 6g iron chloride are joined in the reaction solution of ether of 80g/L vinyl sulfonic acid of 1L; under the condition of nitrogen protection, react 18h at 80 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 19% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 10%, and ammonia can reduce by 12%, and nitrosamine can reduce by 16%.
Embodiment 14
40g mono-cellulose acetate and 9g ABVN are joined in the reaction solution of the acrylic acid acetonitrile of 90g/L of 1L; under the condition of nitrogen protection, react 12h at 60 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 33% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 13%, and ammonia can reduce by 14%, and nitrosamine can reduce by 12%.
Embodiment 15
80g cellulose diacetate and 5g methyl ethyl ketone peroxide are joined in the reaction solution of pyridine of 100g/L maleic acid of 1L; under the condition of nitrogen protection, react 24h at 50 ℃, after water and ethanol clean repeatedly; vacuum drying, obtains percent grafting 20% modification cellulose acetate.Gained modification cellulose acetate is added in filter tip, the cigarette product finally making, through flue gas inspection, its tar can reduce by 13%, and ammonia can reduce by 15%, and nitrosamine can reduce by 21%.
Claims (6)
1. the preparation method of an anionic polymer modification cellulose acetate, it is characterized in that concrete reaction is as follows: monomer is dissolved in in solvent, to be made into concentration be 1-100g/L monomer solution, then add cellulose acetate, the volume ratio of cellulose acetate addition and monomer solution is 0.1-100g/L, add initator simultaneously, under nitrogen protection, react, reaction temperature is 50-100 ℃, reaction time is 0.5-24h, after having reacted, product separation is purified, obtain cationic polymer modification cellulose acetate; Initator addition and monomer solution volume ratio 0.01g/L-10g/L;
Described monomer is at least containing the undersaturated monomer of a kind of mono-vinyl, and this monomer is with sulfonic group or carboxyl.
2. the preparation method of anionic polymer modification cellulose acetate according to claim 1, is characterized in that described cellulose acetate is a cellulose acetate or cellulose diacetate, and its hydroxyl degree of acetylation is 0-2.8.
3. the preparation method of anionic polymer modification cellulose acetate according to claim 1, is characterized in that described monomer is acrylic acid, methacrylic acid, cinnamic acid, maleic acid, styrene sulfonic acid, vinyl sulfonic acid or 2-acrylamide-2-methyl propane sulfonic.
4. the preparation method of anionic polymer modification cellulose acetate according to claim 1, is characterized in that described initator is azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl, hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, potassium permanganate, ammonium ceric nitrate, potassium bichromate or iron chloride.
5. the preparation method of cationic polymer modification cellulose acetate according to claim 1, it is characterized in that described solvent is water, ethanol, methyl alcohol, benzene,toluene,xylene, carrene, dichloroethanes, chloroform, n-hexane, cyclohexane, ether, acetone, acetonitrile, oxolane, pyridine, dimethyl sulfoxide (DMSO), N, dinethylformamide or DMA.
6. the prepared anionic polymer modification cellulose acetate of claim 1 is as the application of preparing cigarette filter stick.
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| CN201410343628.1A CN104126870B (en) | 2014-07-18 | 2014-07-18 | A kind of anionic polymer is modified the preparation method and applications of cellulose acetate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003295A (en) * | 2017-12-15 | 2018-05-08 | 佛山东燊金属制品有限公司 | A kind of preparation method of modified cellulose acetate |
| CN108421535A (en) * | 2018-05-30 | 2018-08-21 | 贾玉臻 | A kind of method of cellulose/hectorite hybrid composite material purification organic wastewater containing phenol |
| CN109864340A (en) * | 2019-04-11 | 2019-06-11 | 滁州卷烟材料厂 | One kind is refreshed oneself the filter tip and preparation method thereof that hawks |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055185A (en) * | 1990-03-24 | 1991-10-09 | 中国科学院广州化学研究所 | Water-absorption material produced by graft modification with cellulose initiated by potassium permanganate |
| CN103193938A (en) * | 2013-05-03 | 2013-07-10 | 云南烟草科学研究院 | Preparation method of modified cellulose acetate |
| CN103601852A (en) * | 2013-11-14 | 2014-02-26 | 云南烟草科学研究院 | Method for modifying cellulose and derivatives thereof |
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2014
- 2014-07-18 CN CN201410343628.1A patent/CN104126870B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055185A (en) * | 1990-03-24 | 1991-10-09 | 中国科学院广州化学研究所 | Water-absorption material produced by graft modification with cellulose initiated by potassium permanganate |
| CN103193938A (en) * | 2013-05-03 | 2013-07-10 | 云南烟草科学研究院 | Preparation method of modified cellulose acetate |
| CN103601852A (en) * | 2013-11-14 | 2014-02-26 | 云南烟草科学研究院 | Method for modifying cellulose and derivatives thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003295A (en) * | 2017-12-15 | 2018-05-08 | 佛山东燊金属制品有限公司 | A kind of preparation method of modified cellulose acetate |
| CN108421535A (en) * | 2018-05-30 | 2018-08-21 | 贾玉臻 | A kind of method of cellulose/hectorite hybrid composite material purification organic wastewater containing phenol |
| CN108421535B (en) * | 2018-05-30 | 2020-09-22 | 温州慧思工业设计有限公司 | Method for purifying phenol-containing organic wastewater by using cellulose/hectorite hybrid composite material |
| CN109864340A (en) * | 2019-04-11 | 2019-06-11 | 滁州卷烟材料厂 | One kind is refreshed oneself the filter tip and preparation method thereof that hawks |
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| CN104126870B (en) | 2018-01-30 |
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