CN105688851B - A kind of preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material - Google Patents

A kind of preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material Download PDF

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CN105688851B
CN105688851B CN201610166222.XA CN201610166222A CN105688851B CN 105688851 B CN105688851 B CN 105688851B CN 201610166222 A CN201610166222 A CN 201610166222A CN 105688851 B CN105688851 B CN 105688851B
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aramid fiber
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amino
polysilsesquioxane
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CN105688851A (en
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曲荣君
王孕峰
张盈
孙昌梅
潘方伟
贾欣桦
纪春暖
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Ludong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4893—Residues derived from used synthetic products, e.g. rubber from used tyres

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Abstract

The problem of present invention after existing polysilsesquioxane absorption heavy metal for being difficult to recycle and the recycling problem of discarded aramid fiber, there is provided a kind of preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material.The beneficial effects of the invention are as follows：The amino polysilsesquioxane para-aramid fiber composite adsorbing material being prepared can improve the utilization rate of adsorbent adsorption function base, the specific surface area that increase adsorbent contacts with solution containing heavy metal ion, so as to improve adsorbance；Become easily extraction easily recovery, while become more stable the chemical property of adsorbent after polysilsesquioxane adsorbent absorption heavy metal can separately be made, while realize the recycling of discarded aramid fiber resource, solve environmental problem caused by heavy metal pollution.

Description

A kind of preparation of amino polysilsesquioxane para-aramid fiber composite adsorbing material Method
Technical field
The present invention relates to a kind of preparation method of adsorbent, more particularly to a kind of preparation method of composite adsorbing material, category In sorbing material technical field.
Background technology
So-called heavy metal refers to the metal that proportion is more than 5, and heavy metal pollution is such as：Water pollution, soil pollution, to dynamic Plant can be caused to damage, and micro heavy metal can gather in human body, and liver kidney and other organs can be caused to damage, at present processing The method of heavy metal pollution mainly have chelating resin method, the precipitation method, polymer chelating agent method, membrane separation technique, charcoal absorption, Natural zeolite absorption method, ion-exchange etc..Heavy metal ion is adsorbed using adsorbent, adsorbance is high, and selectivity is good, absorption Speed is increasingly becoming the focus of research soon.
Containing the polysilsesquioxane of adsorption function base as adsorbent, adsorbance is high, and inexpensively, efficiently, the rate of adsorption is fast, Chemical property is stable, is always the hot topic as adsorbent research.But granular polysilsesquioxane adsorbent absorption weight After metal, it is difficult to recycle, while silicon oxygen bond internal crosslinking can cover adsorption function base, make adsorption function group contacts The area of solution reduces, and makes the utilization rate of adsorption function base reduce.
Aramid fiber has in space flight and aviation and military project etc. and is widely applied very much as a kind of emerging high polymer material, Simultaneous aramid fiber is applied extensive, and some discarded aramid fibers also produce therewith, acidproof because aramid fiber is heat-resist Alkaline-resisting, corrosion-resistant, conventional method is difficult to handle, and it is landfill to handle the most important method of aramid fiber now, therefore will can give up Adsorbent of the aramid fiber as processing heavy metal pollution is abandoned, plays its corrosion resistant effect, while make adsorbent heavy Metal ion becomes easily extraction easily recovery, while solves the problems, such as that discarded aramid fiber recycles.
Thus amino polysilsesquioxane is combined with both aramid fibers, the contraposition of amino polysilsesquioxane is made Aramid fiber composite adsorbing material, can either improve the utilization rate of adsorption function group, while improve adsorbance, fibrous suction Attached dose also can preferably recycle heavy metal resources, and can better profit from discarded aramid fiber, can solve well Certainly heavy metal pollution problem, realize that resource reclaim recycles.
The content of the invention
The problem of present invention after existing polysilsesquioxane absorption heavy metal for being difficult to recycle and discarded aramid fiber are fine A kind of recycling problem of dimension, there is provided preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material, it is characterised in that bag Include following steps：
1) para-aramid fiber is used into toluene, acetone and ethanolic extraction respectively, dried；
2) NaH mixed with anhydrous dimethyl sulphoxide under nitrogen protection, stirring reaction is to being changed into transparent at 60~70 DEG C After solution, cooling；
3) para-aramid fiber obtained by step 1), described NaH and p-aramid fiber are added into step 2) resulting solution The mol ratio of fiber is 1：1~1：10, stirred at 25~30 DEG C, aramid fiber surface is metallized, after 6~12 hours Epoxychloropropane being added thereto substitution reaction occurring, the mol ratio of the epoxychloropropane and NaH is 1：1, will after having reacted Products obtained therefrom is with drying to obtain product I after ethanolic extraction；
4) step 3) products obtained therefrom I being mixed with amino silicane coupling agent under nitrogen protection, dimethyl sulfoxide (DMSO) is solvent, The amino silicane coupling agent and NaH in step 2) mol ratio are 1：1~10：Stirring reaction at 1,60~80 DEG C, by gained Product is with drying to obtain product II after ethanolic extraction；
5) step 4) products obtained therefrom II is mixed with amino silicane coupling agent under nitrogen protection, dimethyl sulfoxide (DMSO) is molten Agent, the amino silicane coupling agent and NaH in step 2) mol ratio are 1：1~16：Stirring reaction at 1,60 DEG C, products obtained therefrom Polymerization is hydrolyzed using sol-gel process, is then aged, is extracted using absolute ethyl alcohol, dry amino polysilsesquioxane Para-aramid fiber composite adsorbing material.
Further, sol-gel process described in step 5) comprises the following steps that：With stirring into reaction products obtained therefrom 4~6ml 0.014g/ml NH is added dropwise4F solution, continue stirring 24 hours after solution stops heat release.
Further, the ageing process described in step 5) is as follows：Digestion time 7~12 days, 60~80 DEG C of temperature.
Further, step 4) and 5) described in amino silicane coupling agent for 3- TSL 8330s, 3- ammonia One kind in base propyl-triethoxysilicane or 3-amino propyl methyl diethoxy silane.
Further, the reaction time of substitution reaction is 12~24 hours in step 3).
Further, the reaction time described in step 4) is 12~48 hours.
Further, the reaction time described in step 5) is 6~12 hours.
The polysilsesquioxane para-aramid fiber being prepared using above-mentioned preparation method is also claimed in the present invention Composite adsorbing material and above-mentioned composite adsorbing material are adsorbing the application in heavy metal field.
The beneficial effects of the invention are as follows：
1) compared with the polysilsesquioxane of bulk, the internal crosslinking of polysilsesquioxane silicon oxygen bond is largely avoid, The amino polysilsesquioxane para-aramid fiber composite adsorbing material being prepared can improve the profit of adsorbent adsorption function base The specific surface area contacted with rate, increase adsorbent with solution containing heavy metal ion, so as to improve adsorbance；
2) easily extraction easily recovery, while make the change of adsorbent is become after polysilsesquioxane adsorbent absorption heavy metal can be made Learn property to become more stable, while realize the recycling of discarded aramid fiber resource, environment caused by solving heavy metal pollution is asked Topic.
Brief description of the drawings
Fig. 1 is the infrared spectrum of para-aramid fiber and the products obtained therefrom of embodiment 1；
Fig. 2 is para-aramid fiber scanning electron microscopic picture；
Fig. 3 is the scanning electron microscopic picture of the products obtained therefrom of embodiment 2；
Fig. 4 is the scanning electron microscopic picture of the products obtained therefrom of embodiment 3；
Fig. 5 is the scanning electron microscopic picture of the products obtained therefrom of embodiment 4；
Fig. 6 is the scanning electron microscopic picture of the products obtained therefrom of embodiment 5；
Fig. 7 is adsorption effect schematic diagram of each embodiment products obtained therefrom to different heavy metal ion；
In Fig. 1, line 1 is the infrared spectrum of para-aramid fiber；Line 2 is the infrared spectrum of the products obtained therefrom of embodiment 1.
Embodiment
The principle and feature of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.
Embodiment 1：
1) para-aramid fiber is put into apparatus,Soxhlet's, it is rearmounted successively with toluene, acetone, ethanolic extraction 24 hours Dried in 60 DEG C of baking oven；
2) after inflated with nitrogen being continued in 250ml three-necked flask 5 minutes, NaH powder 0.4054g is added into three-necked flask (17mmol), 150ml dimethyl sulfoxide (DMSO)s (2100mmol) are then added thereto, be warming up under 70 DEG C of stirring conditions and react 50 points Clock, after solution is changed into clear pale yellow color solution, it is cooled to 30 DEG C；
3) para-aramid fiber obtained by 4g steps 1), para-aramid fiber and NaH are added into step 2) resulting solution Mol ratio be 1：1,1.3ml epoxychloropropane is added after being reacted 6 hours under the conditions of 30 DEG C thereto substitution reaction, ring occurs Oxygen chloropropane and NaH mol ratio are 1：1, continue that products obtained therefrom ethanolic extraction 24 hours is placed in into baking after reaction 24 hours Product I is dried to obtain in case；
4) product I is added in the three-necked flask of the 250ml full of nitrogen, 150ml dimethyl is added into flask The 3- TSL 8330s of sulfoxide solvent and 3g, 3- TSL 8330s and NaH mol ratio are 1： 1, stirring reaction 48 hours at 60 DEG C, by products obtained therefrom ethanolic extraction 24 hours, it is placed in baking oven and dries to obtain product II；
5) 120ml dimethyl sulfoxide solvent is added into the 250ml three-necked flasks full of nitrogen, production is added into flask The 3- TSL 8330s of product II and 30g, 3- TSL 8330s and NaH mol ratio are 10：1, Stirring reaction 12 hours at 60 DEG C, take out resulting solution and fiber is placed in beaker, add 0.014g/ml NH thereto4F Continue stirring 24 hours after solution 5ml, reactant and solvent are transferred in polypropylene vial are aged 7 under the conditions of 80 DEG C afterwards My god, aramid fiber is taken out, extracted 80 hours with absolute ethyl alcohol, is placed in dry amino polysilsesquioxane in vacuum drying chamber Para-aramid fiber composite.
Embodiment 2：
1) para-aramid fiber is put into apparatus,Soxhlet's, it is rearmounted successively with toluene, acetone, ethanolic extraction 24 hours Dried in 60 DEG C of baking oven；
2) after inflated with nitrogen being continued in 250ml three-necked flask 5 minutes, NaH powder 0.4054g is added into three-necked flask (17mmol), 100ml dimethyl sulfoxide (DMSO)s (1400mmol) are then added thereto, be warming up under 70 DEG C of stirring conditions and react 50 points Clock, after solution is changed into clear pale yellow color solution, it is cooled to 30 DEG C；
3) para-aramid fiber obtained by 8g steps 1), para-aramid fiber and NaH are added into step 2) resulting solution Mol ratio be 2：1, substitution reaction occurs for the epoxychloropropane for adding 1.3ml after being reacted 8 hours under the conditions of 30 DEG C thereto, Epoxychloropropane and NaH mol ratio are 1：1, continue to be placed in products obtained therefrom ethanolic extraction 24 hours after reaction 12 hours Product I is dried to obtain in baking oven；
4) product I is added in the three-necked flask of the 250ml full of nitrogen, 150ml dimethyl is added into flask The 3- TSL 8330s of sulfoxide solvent and 6g, 3- TSL 8330s and NaH mol ratio are 2： 1, stirring reaction 36 hours at 70 DEG C, by products obtained therefrom ethanolic extraction 24 hours, it is placed in baking oven and dries to obtain product II；
5) into the 250ml three-necked flasks full of nitrogen add 120ml dimethyl sulfoxide solvent, backward flask in add Enter product II and 15g 3- TSL 8330s, 3- TSL 8330s and NaH mol ratio are 5： Stirring reaction 8 hours under the conditions of 1,60 DEG C, take out resulting solution and fiber is placed in beaker, add 0.014g/ml's thereto NH4Continue stirring 24 hours after F solution 5ml, reactant and solvent are transferred in polypropylene vial afterwards old under the conditions of 70 DEG C Change 9 days, aramid fiber is taken out, extracted 80 hours with absolute ethyl alcohol, be placed in dry the poly- sesquialter silicon of amino in vacuum drying chamber Oxygen alkane para-aramid fiber composite.
Embodiment 3：
1) para-aramid fiber is put into apparatus,Soxhlet's, it is rearmounted successively with toluene, acetone, ethanolic extraction 24 hours Dried in 60 DEG C of baking oven；
2) after inflated with nitrogen being continued in 250ml three-necked flask 5 minutes, NaH powder 0.4054g is added into three-necked flask (17mmol), 200ml dimethyl sulfoxide (DMSO)s (2800mmol) are then added thereto, be warming up under 70 DEG C of stirring conditions and react 50 points Clock, after solution is changed into clear pale yellow color solution, it is cooled to 30 DEG C；
3) para-aramid fiber obtained by 40g steps 1), para-aramid fiber and NaH are added into step 2) resulting solution Mol ratio be 10：1, substitution occurs for the epoxychloropropane for adding 1.3ml after being reacted 10 hours under the conditions of 30 DEG C thereto instead Should, epoxychloropropane and NaH mol ratio are 1：1, continue to put products obtained therefrom ethanolic extraction 24 hours after reaction 18 hours Product I is dried to obtain in baking oven；
4) product I is added in the three-necked flask of the 250ml full of nitrogen, 150ml dimethyl is added into flask The APTES of sulfoxide solvent and 15g, APTES and NaH mol ratio are 5： 1, stirring reaction 24 hours at 75 DEG C, by products obtained therefrom ethanolic extraction 24 hours, it is placed in baking oven and dries to obtain product II；
5) into the 250ml three-necked flasks full of nitrogen add 120ml dimethyl sulfoxide solvent, backward flask in add Enter product II and 39g APTES, APTES and NaH mol ratio are 13：1, stirring reaction 6 hours under the conditions of 60 DEG C, take out resulting solution and fiber is placed in beaker, add 0.014g/ thereto Ml NH4Continue stirring 24 hours after F solution 6ml, reactant and solvent are transferred in polypropylene vial in 75 DEG C of conditions afterwards Lower ageing 8 days, aramid fiber is taken out, and is extracted 80 hours with absolute ethyl alcohol, is placed in dry that amino is poly- again in vacuum drying chamber Half siloxanes para-aramid fiber composite.
Embodiment 4：
1) para-aramid fiber is put into apparatus,Soxhlet's, it is rearmounted successively with toluene, acetone, ethanolic extraction 24 hours Dried in 60 DEG C of baking oven；
2) after inflated with nitrogen being continued in 250ml three-necked flask 5 minutes, NaH powder 0.4054g is added into three-necked flask (17mmol), 150ml dimethyl sulfoxide (DMSO)s (2100mmol) are then added thereto, be warming up under 70 DEG C of stirring conditions and react 50 points Clock, after solution is changed into clear pale yellow color solution, it is cooled to 25 DEG C；3) 20g steps 1) institute is added into step 2) resulting solution The para-aramid fiber obtained, para-aramid fiber and NaH mol ratio are 5：1, reacted under the conditions of 25 DEG C 12 hours it is backward its Middle addition 1.3ml epoxychloropropane generation substitution reaction, epoxychloropropane and NaH mol ratio are 1：1, continue reaction 20 hours Afterwards by products obtained therefrom ethanolic extraction 24 hours, it is placed in baking oven and dries to obtain product I；
4) product I is added in the three-necked flask of the 250ml full of nitrogen, 150ml dimethyl is added into flask The APTES of sulfoxide solvent and 21g, APTES and NaH mol ratio are 7： 1, stirring reaction 30 hours at 80 DEG C, by products obtained therefrom ethanolic extraction 24 hours, it is placed in baking oven and dries to obtain product II；
5) into the 250ml three-necked flasks full of nitrogen add 120ml dimethyl sulfoxide solvent, backward flask in add Enter product II and 3g APTES, APTES and NaH mol ratio are 1： 1, stirring reaction 12 hours under the conditions of 60 DEG C, take out resulting solution and fiber is placed in beaker, add 0.014g/ml thereto NH4Continue stirring 24 hours after F solution 4ml, reactant and solvent are transferred in polypropylene vial under the conditions of 60 DEG C afterwards Ageing 12 days, aramid fiber is taken out, and is extracted 80 hours with absolute ethyl alcohol, is placed in dry the poly- sesquialter of amino in vacuum drying chamber Siloxanes para-aramid fiber composite.
Embodiment 5：
1) para-aramid fiber is put into apparatus,Soxhlet's, it is rearmounted successively with toluene, acetone, ethanolic extraction 24 hours Dried in 60 DEG C of baking oven；
2) after inflated with nitrogen being continued in 250ml three-necked flask 5 minutes, 0.4054g NaH powder is added into three-necked flask End, 150ml dimethyl sulfoxide (DMSO)s are then added thereto, is warming up under 70 DEG C of stirring conditions and reacts 50 minutes, treat that solution is changed into After bright yellow solution, 30 DEG C are cooled to；
3) para-aramid fiber obtained by 15g steps 1), para-aramid fiber and NaH are added into step 2) resulting solution Mol ratio be 5：1, substitution occurs for the epoxychloropropane for adding 1.3ml after being reacted 12 hours under the conditions of 30 DEG C thereto instead Should, epoxychloropropane and NaH mol ratio are 1：1, continue to put products obtained therefrom ethanolic extraction 24 hours after reaction 24 hours Product I is dried to obtain in baking oven；
4) product I is added in the three-necked flask of the 250ml full of nitrogen, 150ml dimethyl is added into flask The 3-amino propyl methyl diethoxy silane of sulfoxide solvent and 30g, 3-amino propyl methyl diethoxy silane and NaH's rubs You are than being 10：1, stirring reaction 48 hours at 65 DEG C, by products obtained therefrom ethanolic extraction 24 hours, it is placed in baking oven and dries Product II；
5) into the 250ml three-necked flasks full of nitrogen add 120ml dimethyl sulfoxide solvent, backward flask in add Enter product II and 48g 3-amino propyl methyl diethoxy silane, 3-amino propyl methyl diethoxy silane and NaH's rubs You are than being 16：1, stirring reaction 12 hours at 60 DEG C, take out resulting solution and fiber is placed in beaker, add thereto 0.014g/ml NH4Continue stirring 24 hours after F solution 5ml, reactant and solvent are transferred in polypropylene vial in 65 afterwards It is aged 12 days under the conditions of DEG C, aramid fiber is taken out, extracted 80 hours with absolute ethyl alcohol, is placed in dry ammonia in vacuum drying chamber Base polysilsesquioxane para-aramid fiber composite.
The concrete operation step of the testing adsorption effect of the products obtained therefrom of embodiment 1~5 is as follows：
Five kinds of sorbing materials 1,2,3,4,5 that quality is the above-mentioned gained of 20mg are weighed respectively, in conical flask with cover, are respectively added Enter 5 × 10-3Mol/L Cu (II), Hg (II), Ag (I) and Pb (II) and 1 × 10-3Mol/L Au (III) aqueous solution 20mL, it is placed in 24 hours of vibration in gas bath oscillator.With the concentration of residual metallic ion in Solution by Atomic Absorption Spectrophotometry.With Formula (1) calculates the adsorbance Q (mmol/g) of sorbing material, and its adsorption effect is as shown in Figure 6.
Wherein Q：The adsorbance (mmol/g) of heavy metal ion；C0：Initial ion concentration (mmol/mL) in solution；Ce： The concentration (mmol/mL) of effects of ion after adsorbent adsorption equilibrium；V：The volume (mL) of solution；W：Adsorbent mass (g).
Fig. 1 is the infrared spectrum of para-aramid fiber and the adsorbent of the preparation of embodiment 1, compared with para-aramid fiber, Prepared adsorbent is in 3400cm-1The absworption peak of left and right, which broadens, is primarily due to amido link N-H stretching vibration peaks and silicone hydroxyl Caused by stretching vibration, in 2925cm-1It is the CH being connected with Si that absworption peak, which occurs, in place2Infrared absorption peak, adsorbent exists 1637cm-1The infrared absorption peak absorption intensity enhancing of left and right, it is because not only having C=O stretching vibration peaks, and SiO here2 The common exercising result of stretching vibration, while in 1042cm-1There is SiO in place2Characteristic absorption peak.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.

Claims (7)

  1. A kind of 1. preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material, it is characterised in that including Following steps：
    1) para-aramid fiber is used into toluene, acetone and ethanolic extraction respectively, dried；
    2) NaH mixed with anhydrous dimethyl sulphoxide under nitrogen protection, stirring reaction is to being changed into clear solution at 60~70 DEG C Afterwards, cool；
    3) para-aramid fiber obtained by step 1), described NaH and para-aramid fiber are added into step 2) resulting solution Mol ratio be 1：1~1：10, stirred at 25~30 DEG C, aramid fiber surface metallized, 6~12 hours it is backward its Substitution reaction occurs for middle addition epoxychloropropane, and the mol ratio of the epoxychloropropane and NaH is 1：1, by gained after having reacted Product is with drying to obtain product I after ethanolic extraction；
    4) step 3) products obtained therefrom I is mixed with amino silicane coupling agent under nitrogen protection, dimethyl sulfoxide (DMSO) is solvent, described Amino silicane coupling agent and NaH in step 2) mol ratio are 1：1~10：Stirring reaction at 1,60~80 DEG C, by products obtained therefrom With drying to obtain product II after ethanolic extraction；
    5) step 4) products obtained therefrom II is mixed with amino silicane coupling agent under nitrogen protection, dimethyl sulfoxide (DMSO) is solvent, institute The mol ratio for stating amino silicane coupling agent and NaH in step 2) is 1：1~16：Stirring reaction at 1,60 DEG C, products obtained therefrom use Polymerization is hydrolyzed in sol-gel process, is then aged, and is extracted using absolute ethyl alcohol, dry that amino polysilsesquioxane aligns Aramid fiber composite adsorbing material；
    Wherein, step 4) and 5) described in amino silicane coupling agent for 3- TSL 8330s, 3- aminopropyls One kind in triethoxysilane or 3-amino propyl methyl diethoxy silane；
    Sol-gel process described in step 5) comprises the following steps that：With stirring 4 are added dropwise into reaction products obtained therefrom~ 6mL 0.014g/mL NH4F solution, continue stirring 24 hours after solution stops heat release.
  2. 2. the preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material according to claim 1, Characterized in that, the ageing process described in step 5) is as follows：Digestion time 7~12 days, 60~80 DEG C of temperature.
  3. 3. the preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material according to claim 1, Characterized in that, the reaction time of substitution reaction is 12~24 hours in step 3).
  4. 4. the preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material according to claim 1, Characterized in that, the reaction time in step 4) is 12~48 hours.
  5. 5. the preparation method of amino polysilsesquioxane para-aramid fiber composite adsorbing material according to claim 1, Characterized in that, the reaction time in step 5) is 6~12 hours.
  6. 6. amino polysilsesquioxane p-aramid fiber prepared by a kind of preparation method as any one of claim 1-5 is fine Tie up composite adsorbing material.
  7. 7. amino polysilsesquioxane para-aramid fiber composite adsorbing material according to claim 6 is in absorption heavy metal In application.
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CN106592220A (en) * 2016-12-24 2017-04-26 中国科学技术大学 Aramid fiber surface modification method
CN109694522B (en) * 2017-10-20 2022-03-29 中国石油化工股份有限公司 Low-VOC low-odor polypropylene resin composition and preparation method thereof
CN108727639B (en) * 2018-06-12 2020-12-11 哈尔滨工业大学 Preparation method and application of bacterial cellulose/aramid nanofiber composite aerogel

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851335A (en) * 2010-05-26 2010-10-06 鲁东大学 Preparation method of dual-functional group modified silica gel adsorptive material and application thereof in metal ion adsorption
CN103193980A (en) * 2013-04-03 2013-07-10 山东大学 Imidazolyl polysilsesquioxane adsorbent material, and preparation method and application thereof
CN103585988A (en) * 2013-10-17 2014-02-19 青岛昊源环境工程技术有限公司 Green environment-friendly cadmium-compound-containing wastewater adsorbing material
CN104624173A (en) * 2015-01-22 2015-05-20 鲁东大学 Preparation method for novel adsorption material based on para-aramid fibers and containing polyamine functional group
CN105268400A (en) * 2015-09-30 2016-01-27 江苏苏通碳纤维有限公司 Method for supporting nanometer titanium dioxide on active carbon fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851335A (en) * 2010-05-26 2010-10-06 鲁东大学 Preparation method of dual-functional group modified silica gel adsorptive material and application thereof in metal ion adsorption
CN103193980A (en) * 2013-04-03 2013-07-10 山东大学 Imidazolyl polysilsesquioxane adsorbent material, and preparation method and application thereof
CN103585988A (en) * 2013-10-17 2014-02-19 青岛昊源环境工程技术有限公司 Green environment-friendly cadmium-compound-containing wastewater adsorbing material
CN104624173A (en) * 2015-01-22 2015-05-20 鲁东大学 Preparation method for novel adsorption material based on para-aramid fibers and containing polyamine functional group
CN105268400A (en) * 2015-09-30 2016-01-27 江苏苏通碳纤维有限公司 Method for supporting nanometer titanium dioxide on active carbon fibers

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Bridged polysilsesquioxane xerogels functionalizated by amine- and thiol- groups: synthesis, structure, adsorption properties;A.Dabrowski et al.;《Adsorption》;20051231;第11卷;第501-517页 *
桥联聚倍半硅氧烷及其在吸附领域中的应用;李春雪等;《离子交换与吸附》;20121031;第28卷(第5期);第469-480页 *

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