CN1843619A - Method for preparing high-selective absorbing and separating fiber material - Google Patents

Method for preparing high-selective absorbing and separating fiber material Download PDF

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CN1843619A
CN1843619A CN 200610066433 CN200610066433A CN1843619A CN 1843619 A CN1843619 A CN 1843619A CN 200610066433 CN200610066433 CN 200610066433 CN 200610066433 A CN200610066433 A CN 200610066433A CN 1843619 A CN1843619 A CN 1843619A
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washing
graft
initiation
fibre
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胡秀峰
周绍箕
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Abstract

The invention discloses a method for preparing new high-selectivity adsorption separation fiber, belonging to the technique of functional macromolecule. The method comprises the steps as washing; pre-induction; using new branch liquid to induce chemical branch aggregation; washing; filtration; and drying. Said method can continuously produce long or short wire, while the wire beam has large specific surface area, high adsorption speed, strong and stable selective adsorption separation ability, non-pollution, stable quality, etc. It can be used to adsorb harmful materials as alkaloid and carbon monoxide, etc.

Description

A kind of preparation method of new high selectivity adsorbing separation fibrous material
Technical field the invention belongs to functional high polymer material field.
Background technology is (Adams BA since middle 1930s, ion exchange resin came out, Holmes EL), fibrous functional material manufacture the attention that obtains people day by day, natural or synthetic fibrous material is applied to the separation and the purification of material, fibrous material divides inorganic functional fiber and organic functions fiber two big classes, the inorganic functional fiber is to be formed by inorganic or organic precursor method fiber production by element-specific component and technology, as activated carbon fiber, pole filter, non-polar fibers etc.; The organic functions fiber is to make by introducing specific function group (organo-functional group or extraordinary trace element) on natural or the synthetic fibers, as ion-exchange fibre, chelating fibre etc.The fibrous material preparation method is different.Such as: professors Feng Changgen of Beijing Institute of Technology etc. (patent No. CN01142191.6) are by series of chemical such as partial carbonization, sulfonation or aminations, specific ionic group is incorporated into makes the yin, yang ion-exchange fibre in the polyvinyl alcohol synthetic fibers, work out again subsequently by pre-irradiation the polypropylene fibre graft phenylethene, and make strongly basic anion ion exchange fibre (number of patent application 200410037778.6) through chloromethylation, amination method; Beijing Institute of Clothing Tech continue in week (patent No. CN98103455.1) such as dustpans by polyolefine fiber at initator, crosslinking agent exists down, aggregate into the ion-exchange fibre matrix with alkenyl benzene, utilize sulfonating agent again, generate strong acidic ion-exchange fiber with the matrix reaction, perhaps utilize the amination of anion imported agent to obtain strong basicity, Weak-alkaline ion exchange fibre, it is characterized in that utilizing earlier sweller to soak polyolefine fiber, flood alkenyl benzene and crosslinking agent again, be added with the free radical protective agent during polymerisation, making alkalescent uses primary amine or secondary amine to do the anion imported agent from exchange fiber the time, improve again subsequently that to work out by natural fiber or chemical fibre be raw fibre, at styrene, divinylbenzene, under the grafting liquid effect that initator is formed, make graft fibres, make through sulfonation by graft fibres and to contain sulfonic strong-acid cation exchange fibre, perhaps under the condition that catalyst exists, graft fibres are imported chloro-methyl group, with multiple organic amine reaction, make anion-exchange fibre (patent No. CN200310101844.7 and CN200310101843.2) again; The inert gas that (patent No. CN93106033.8) such as the Fu Ruowen of Zhongshan University replaces with water vapour using in the past is as protecting gas to prepare the method for activated carbon fiber, and Chinese etc. (patent No. CN00117568.8) once, adopt the method for organic polyacrylonitrile fibre chemical modification to prepare the method for New-type wide-spectrum antibacterial functions fiber, comprise that fiber floods in hydrazine hydrate solution, process such as amidrazone structuring and basic hydrolysis; Inst. of Chemistry, He'nan Prov. Academy of Sciences former think of state (patent No. CN95116025.7) etc. provides and adopted general goods acrylic fiber, polyethylene polyamine is a kind of acid-gas adsorbing fibre of raw material and preparation method thereof, and the polyhydric alcohol solutions that adopts acrylic fiber and polyethylene polyamine react intermediate product, intermediate product carries out the functional group modification and makes a kind of chelating function fiber synthetic method (patent No. CN98119070.7) etc. in aqueous hydroxylamine solution or alcoholic solution.
Yet, can be used in the preparation method that selective absorption separates cigarette smoke tar and harmful substance thereof and keep the high selectivity adsorbing separation fibrous material of fragrant jealous composition and still be not reported.As seen, high selectivity adsorbing separation cigarette smoke tar that the present invention goes out and harmful substance thereof and keep fragrant jealous composition the efficient selective fibrous material the preparation method not only to the development new functional macromolecule material have positive effect, also to produce novel stable performance in batches, free of contamination efficient selective adsorbing fiber material has realistic meaning.
Summary of the invention the present invention relates to adopt washing, causes in advance, novel grafting liquid causes the chemical graft polymerization, filtration, drip washing are filtered, dry or the like a series of chemistry and physical method prepare high selectivity adsorbing separation fibrous material.This method be with synthetic fibers by organic solvent washing, pre-cause, novel grafting liquid chemical reagent causes, specific function functional group or element-specific are introduced in glycerol polymerization at a certain temperature in fiber, a series of chemistry such as process filtration then, drip washing filtration, drying and physical method become synthetic fibers to have the high selectivity adsorption separation performance.Owing to handle through glycerol polymerization formula of liquid polymerization process and the pre-treatment process that causes, not only the selective absorption physical capacity is strong, adsorption rate is fast for this high selectivity adsorbing separation fibrous material, pollution-free, and the novel environment friendly high selectivity adsorbing separation fibrous material of tow steady quality, shredding is functional, cutting performance is good, antistatic property is excellent, the tow tieing is few a kind of function admirable, simultaneously this high selectivity adsorbing separation fibrous material have that specific area is big, features such as acid and alkali-resistance, water-fast, organic solvent-resistant, heat-resisting, favorable mechanical performance.The suitability for industrialized production of this high selectivity adsorbing separation fibrous material is convenient in the preparation method's of this new high selectivity adsorbing separation fibrous material invention, has that production technology is simple, cost is low, characteristics with short production cycle, free of contamination.
The preparation method of high selectivity adsorbing separation fibrous material of the present invention comprises that washing, pre-initiation, novel grafting liquid cause synthesis technique steps such as chemical graft polymerization, filtration, drip washing filtration, drying, and is specific as follows:
Can select raw material for use: synthetic fiber material (as polypropylene fibre, polyacrylonitrile fibre etc., it is the synthetic fiber material polypropylene fibre of 1.0~8.4dtex that the embodiment of the invention is selected fiber number); Divinylbenzene (chemical pure); Benzoyl peroxide (chemical pure); Azodiisobutyronitrile (chemical pure); Tirethylene glycol (technical grade); Glycol monoethyl ether (technical grade); Ethylene glycol (technical grade); Toluene (technical grade); Dimethylbenzene (technical grade); Dichloroethanes (technical grade); NaOH (technical grade); Sodium chloride (technical grade); Methacrylic acid (technical grade); Acrylic acid (technical grade); Itaconic acid (technical grade); Maleic acid (technical grade); Ethanol (technical grade);
With polypropylene fibre (POLYPROPYLENE FIBER PP) is the preparation of the high selectivity adsorbing separation fibrous material of matrix:
(1) washing: polypropylene fibre (PP) was soaked 1~15 minute in concentration is 2~30% acetone soln.Acetone solution reclaims and treats to use again.
(2) the pre-initiation: the polypropylene fibre after will washing (PP) is immersed in the mixed liquor that contains chemical initiator (as: benzoyl peroxide) and interfacial agents (as: saturated aqueous common salt) and soaked 1~15 minute.
(3) cause the chemical graft polymerization: will soak and under 50~100 ℃ of temperature, carry out graft polymerization reaction at the initiation grafting liquid for preparing, 0.5~6.0 hour graft polymerization reaction time after back polypropylene fibre (PP) discharges acetone after filtration.
(4) filter: the graft fibres after the initiation grafting polymerisation discharge initiation grafting liquid after filtration, 1~15 minute time spent.Grafting liquid reclaims and treats to use again.
(5) drip washing is filtered: the graft fibres that will discharge initiation grafting liquid are gone ahead of the rest and are washed after the ethanol drip washing, till the pH neutrality, filter the release cleaning solution then, 1~15 minute time spent.The cleaning solution recycling is treated to use again.
(6) drying: will carry out drying through tortuous graft fibres, baking temperature gets finished product at 40~70 ℃ after the constant weight.
Compare with other sorbing material, the advantage of fibrous material of the present invention is:
(1) but both serialization industrial production prepare long filament, but the short silk of also serialization industrial production preparation, preparation technology is simple, cost is low, and is with short production cycle, do not produce pollution in the production process.
(2) selective adsorption capacity is strong, conveniently be used in gas separation aspect, can in divided gas flow, have outstanding performance aspect the gas harmful substances (comprising the cigarette smoke harmful substance) such as many lopps material, alkaloid, carbon monoxide, specific area is big, specific area is 15~20 times of granular resin, and exchange capacity is 30~50 times of resin.
(3) not only have the high selectivity adsorption capacity, and have the advantage of fiber, diameter is little, and the exchange adsorption process has very significantly penetration power, and adsorption rate is fast, and is pollution-free.
(4) tow steady quality, shredding is functional, and cutting performance is good, the antistatic property excellence, the tow tieing is few, and mechanical strength is good, has acid and alkali-resistance, water-fast, organic solvent-resistant, characteristic such as heat-resisting.
Therefore (5) because material is a kind of continuous long filament, can be made into cloth with common textile machine or weaves into net, be difficult to produce plug-hole and organic contamination, swelling capacity only 1.2% relatively, can adapt to various forms of separating substances processes.Reproduction speed is fast, and does not influence the selective absorption separating power.
The specific embodiment has been produced respectively with polypropylene fibre (POLYPROPYLENE FIBER by preparation method of the present invention, PP) be the high selectivity adsorbing separation fibrous material of matrix, the raw material proportioning of producing sees Table 1, the synthesis technique of producing sees Table 2, and the key property of the high selectivity adsorbing separation fibrous material of production sees Table 3.
The raw material proportioning that table 1 is produced
Batching Lot number 1 Lot number 2
Synthetic fiber material The basic fiber of polypropylene (PP), monofilament linear density 4.29 dtex The basic fiber of polypropylene (PP), monofilament linear density 3.4dtex
Divinylbenzene Consumption (PP relatively) 15% Consumption (PP relatively) 15%
Azodiisobutyronitrile Concentration 2% /
Benzoyl peroxide / Concentration 2%
Ethylene glycol Concentration 17% Concentration 17%
Toluene Concentration 20% Concentration 20%
Acrylic acid / Concentration 40%
Sodium chloride (saturated) Bath raio is about 1: 40 Bath raio is about 1: 40
Methacrylic acid Concentration 45% /
Ethanol drip washing Bath raio is about 1: 60 Bath raio is about 1: 60
The synthesis technique time course of table 2 high selectivity adsorbing separation fibrous material preparation
Figure A20061006643300061
The key property of two batches of high selectivity adsorbing separation fibrous materials that table 3 is produced
Figure A20061006643300062

Claims (4)

1, a kind of high selectivity adsorbing separation fibrous material preparation method relates to and can select raw material for use:
Synthetic fiber material (as polypropylene fibre, polyacrylonitrile fibre etc.); Divinylbenzene; Benzoyl peroxide; Azodiisobutyronitrile; Tirethylene glycol; Glycol monoethyl ether; Ethylene glycol; Toluene; Dimethylbenzene; Dichloroethanes; NaOH; Sodium chloride; Methacrylic acid; Acrylic acid; Itaconic acid; Maleic acid; Ethanol.
And adopt following preparation method:
(1) washing: polypropylene fibre (PP) was soaked 1~15 minute in concentration is 2~30% acetone soln.Acetone solution reclaims and treats to use again.
(2) the pre-initiation: the polypropylene fibre after will washing (PP) is immersed in the mixed liquor that contains chemical initiator (benzoyl peroxide) and interfacial agents (saturated aqueous common salt) and soaked 1~15 minute.
(3) cause the chemical graft polymerization: will soak and under 50~100 ℃ of temperature, carry out graft polymerization reaction at the initiation grafting liquid for preparing, 0.5~6.0 hour graft polymerization reaction time after back polypropylene fibre (PP) discharges acetone after filtration.
(4) filter: the graft fibres after the initiation grafting polymerisation discharge initiation grafting liquid after filtration, 1~15 minute time spent.Grafting liquid reclaims and treats to use again.
(5) drip washing is filtered: the graft fibres that will discharge initiation grafting liquid are gone ahead of the rest and are washed after the ethanol drip washing, till the pH neutrality, filter the release cleaning solution then, 1~15 minute time spent.The cleaning solution recycling is treated to use again.
(6) drying: graft fibres are carried out drying, and baking temperature gets finished product at 40~70 ℃ after the constant weight.
2, be to be matrix with the composite fibre materials according to the described high selectivity adsorbing separation of claim 1 fibrous material, by grafting, the high polymer of diameter 2~50 μ m that introduce cation exchange groups and make, can reach the purpose of harmful substances such as many lopps material, alkaloid, carbon monoxide in the selective absorption divided gas flow by the principle of chemisorbed and physical absorption, especially be applied in harmful substances such as tarry matters in smoke, carbon monoxide, nicotine are separated and to keep the jealous composition of original perfume (or spice) aspect performance outstanding.But produce graft fibres long filament or short silk with the inventive method serialization industrial preparation.
3, described pre-initiation is a novel preparation process feature of the present invention according to claim 1, synthetic fibers is immersed in soaked in the mixed liquor that contains chemical initiator and interfacial agents 1~15 minute.
4, the grafting liquid compositing formula that the present invention relates to comprises that the embodiment of recommendation has obtained detailed description here.This example helps to understand the present invention, but can not be interpreted as restriction the present invention.Should be proficient in the people of this area for those, the above-mentioned method according to the present invention, can make many variations and/or improvement to the present invention, the every any ratio prescription that can select for use raw material to form for matter utilization the present invention in the selective absorption divided gas flow is preparing graft fibres still within claim scope given to this invention on the synthetic fibers.
CN 200610066433 2006-03-31 2006-03-31 Method for preparing high-selective absorbing and separating fiber material Pending CN1843619A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101632918B (en) * 2008-07-22 2012-07-04 天津博纳艾杰尔科技有限公司 Grafting fiber material with adsorptive action and use method thereof
CN102587117A (en) * 2012-02-28 2012-07-18 中国科学院上海应用物理研究所 Amidoxime-based chelate polyacrylonitrile fiber and its preparation method and application
CN102631954A (en) * 2012-03-06 2012-08-15 淮海工学院 Chelation ion exchange fiber capable of resisting marine organism stain and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101632918B (en) * 2008-07-22 2012-07-04 天津博纳艾杰尔科技有限公司 Grafting fiber material with adsorptive action and use method thereof
CN102587117A (en) * 2012-02-28 2012-07-18 中国科学院上海应用物理研究所 Amidoxime-based chelate polyacrylonitrile fiber and its preparation method and application
CN102631954A (en) * 2012-03-06 2012-08-15 淮海工学院 Chelation ion exchange fiber capable of resisting marine organism stain and preparation method thereof
CN102631954B (en) * 2012-03-06 2014-05-14 淮海工学院 Chelation ion exchange fiber capable of resisting marine organism stain and preparation method thereof

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