CN101565481B - Method for preparing methanol absorbent polymer - Google Patents

Method for preparing methanol absorbent polymer Download PDF

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CN101565481B
CN101565481B CN2009101077071A CN200910107707A CN101565481B CN 101565481 B CN101565481 B CN 101565481B CN 2009101077071 A CN2009101077071 A CN 2009101077071A CN 200910107707 A CN200910107707 A CN 200910107707A CN 101565481 B CN101565481 B CN 101565481B
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polystyrene
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CN101565481A (en
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朱光明
韦业林
王雷
莫惠明
张庭亮
吴凤
熊小义
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Shenzhen University
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Abstract

本发明适用于甲醇吸收剂领域，提供了一种甲醇吸收剂聚合物的制备方法，以聚苯乙烯为原料，通过氯甲基化反应或者氯乙酰化反应，在苯环上接上含氯甲基或氯乙酰基团，然后通过季铵化反应，制备成聚苯乙烯胺基树脂。该聚苯乙烯胺基树脂所具备的优点是：将其浸泡在液态甲醇或甲醇蒸汽中，可吸收自身质量几倍至几百倍的甲醇。The invention is applicable to the field of methanol absorbent, and provides a method for preparing a methanol absorbent polymer. Using polystyrene as a raw material, chloromethylation or chloroacetylation is used to connect benzene rings with methyl chloride group or chloroacetyl group, and then prepared into polystyrene amine-based resin by quaternization reaction. The polystyrene amine-based resin has the advantage that it can absorb several to several hundred times its own mass of methanol when soaked in liquid methanol or methanol vapor.

Description

The preparation method of methanol absorbing agent polymer
Technical field
The present invention relates to the functional polymer field, relate to a kind of preparation method that can absorb the polymkeric substance of methyl alcohol in a large number specifically.
Background technology
Methanol absorbing agent is widely used in methyl alcohol on chemical industry absorption with separate.In fuel cell field, methanol absorbing agent also can be used for making the fuel cassette (cartridge) of DMFC, makes the methyl alcohol that is stored in wherein be the solid absorbing state, increases accessibility and security that pile uses.Methanol absorbing agent also can be used for absorption refrigeration.Absorbing refrigeration system is mainly formed " working medium to " by solid adsorption material and refrigeration agent, by used heat or Driven by Solar Energy, can be made into novel energy-conserving air-conditioning or ice-making machine.Gac/methyl alcohol is to be considered to absorption refrigeration most effective a group " working medium to " at present [to see also document: (1) P.O ' D.Offenhartz et al; J.Sol.Energy Eng.s Trans.ASME 1980,102,59; (2) H.Lai et al, Chem.Eng.Sci.1996,51,2951; (3) F.Meunie et al; Applied Thermal Engineering 1998,18,715; (4) L.W.Wang et al., Applied Thermal Engineering 2003,23,1605].
Activated carbon and zeolite are the methanol absorbing agents of using always, but their methyl alcohol absorbed doses when room temperature have only 0.15～0.25 and 0.14～0.18 gram/gram respectively, and the methyl alcohol absorbed dose is limited.In order to improve the methyl alcohol absorbed dose, in the last few years, people had synthesized a kind of new methanol absorbing agent, and it is at LiCl, CaCl with silica gel 2Soak in the aqueous solution Deng halogen, the product of dry gained about 200 ℃ is called the salt (Saltsin Mesoporous Silica) in the mesopore silicon oxide then.When halogen was LiCl, the methyl alcohol absorbed dose was 2.25 gram/grams (LiCl); Be CaCl 2The time, the methyl alcohol absorbed dose is 0.58 gram/gram (CaCl 2).The mechanism that they absorb methyl alcohol is respectively:
LiCl+3CH 3OH＝LiCl·3CH 3OH
CaCl 2+2CH 3OH＝CaCl 2·2CH 3OH
This type material is as counting the quality of mesopore silicon oxide, and the methyl alcohol absorbed dose is also little.
Summary of the invention
The purpose of the embodiment of the invention is to provide a kind of preparation method of methanol absorbing agent polymer, is intended to solve the existing little problem of methanol absorbing agent methyl alcohol absorbed dose.
The embodiment of the invention is achieved in that a kind of preparation method of methanol absorbing agent polymer, and this method is raw material with the PS, through chloromethylation or chlorine acetylation, on phenyl ring, connects and contains chloromethyl (CH 2Cl) or chloracetyl (CO-CH 2Cl) group through quaterisation, is prepared into the PS amine resin then.
Compared with prior art, the advantage that the resulting PS amine resin of technique scheme is possessed is: it is immersed in liquid methanol or the methanol steam, can absorbs several times of methyl alcohol to hundred times of sole mass.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
For solving the existing little problem of methanol absorbing agent methyl alcohol absorbed dose; The embodiment of the invention provides a kind of preparation method of methanol absorbing agent polymer; This method is raw material with the PS, through chloromethylation or chlorine acetylation, on phenyl ring, connects and contains chloromethyl (CH 2Cl) or chloracetyl (CO-CH 2Cl) group through quaterisation, is prepared into amine resin then.
Particularly, the preparation method of the polymkeric substance methanol absorbing agent of the embodiment of the invention may further comprise the steps:
(1) gets PS, polystyrene solution is processed in its dissolving;
(2) in step (1) resulting polymers solution, add chloromethylation reagent or chloroacetylation reagent, add-on is not less than 0.05 times of polymer poly vinylbenzene mole number in the solution;
(3) in step (2) gained solution, add Louis (Lewis) acid catalyst, add-on is step (2) institute's chlorination methylating reagent or chloroacetylation reagent mole number 1～6 times, mixes and reacts;
(4) step (3) gained reaction solution is poured in the hydrochloric acid soln, after mixing, added ethanol and separate out product;
(5) step (4) gained precipitate is soaked after drying in quaternizing agent or its solution, remove unnecessary unreacted quaternizing agent or quaternizing agent solution and get the PS amine resin.
More specifically, wherein, step (3) reaction can be carried out under heating condition, and with the shortening reaction times, but Heating temperature is no more than the boiling point of solvent in the said polystyrene solution of step (1); Step (3) reaction also can be carried out under the cooling condition, and with the generation of minimizing side reaction, but Heating temperature is not less than the freezing point of solvent in the said polystyrene solution of step (1).General control reaction temperature is-10～60 ℃, and the reaction times is 0.5～24 hour.
More specifically, wherein, step (4) concentration of hydrochloric acid solution is preferably 0.05～5M.
More specifically, wherein, step (5) is before afterwards for step (4); The gained precipitate filters in advance, leaches thing and cleans with zero(ppm) water and ethanol, generally respectively washes twice; Order is any, soaks general 1～24 hour at least 1 hour with zero(ppm) water and alcohol mixeding liquid again; Filtered the final vacuum drying at least 1 hour, general 1～48 hour.Wherein, zero(ppm) water and alcohol mixeding liquid volume ratio be preferably 1: 5～5: 1.Like this, can improve product purity.
More specifically, wherein, in the step (5); Step (4) products therefrom was soaked 6 hours in quaternizing agent or its solution at least, general 6～72 hours, took out the final vacuum drying at least 12 hours; General 12～72 hours, again with deionized water or organic solvent washing by soaking, general 2～20 times; And then 40～60 ℃ of vacuum-drying at least 1 hour, general 1～48 hour.Wherein, said organic solvent does not have special restriction, by being used always this area, is the saving cost, preferred low boiling point organic solvent, and for example, the mixing of one or more in methyl alcohol, ethanol, Virahol, acetone, the ether is so that vacuum-drying removes.
More specifically, wherein, in the step (1) solvent of polystyrene solution be any solubilized or swelling PS but not with the organic cpds of PS, said chloromethylation reagent or said chloroacetylation reagent react; Preferred trichloromethane (chloroform), methylene dichloride, 1,2-ethylene dichloride, 1,1; 2, and 2-tetrachloroethane, dithiocarbonic anhydride, sherwood oil, oil of mirbane, N-Methyl pyrrolidone (N-methyl-2-pyrrolidone, NMP), DMSO 99.8MIN. (DMSO; Dimethyl sulfoxide), N, dinethylformamide (DMF; Dimethylformamide), DMAC N,N (DMAc; N, the mixing of one or more in N-dimethylacetamide).
Chloromethylation reagent is meant in the step (2): concentration is that mixture, trimethylchlorosilane and the polymerization degree of 8～100 Paraformaldehyde 96 is the mixture or the chloromethyl hydrocarbyl ether of 8～100 Paraformaldehyde 96 greater than the concentrated hydrochloric acid of 12M and the polymerization degree.Wherein, The chloromethyl hydrocarbyl ether is preferred: 1; 1-dichlormethyl ether (dichloromethyl ether), chloromethyl methyl ether, chloromethyl ether, chloromethyl propyl ether, chloromethyl butyl ether, chloromethyl amyl ether, chloromethyl hexyl ether, chloromethyl Octyl Ether, 1; The mixing of one or more in the 4-dichloro methyl butyl ether [1,4-bis (chloromethoxyl) butane, BCMB].Chloroacetylation reagent is monochloro-acetyl chloride;
Lewis acid catalyst is meant aluminum chloride (AlCl in the step (3) 3), zinc dichloride (ZnCl 2), iron trichloride (FeCl 3), tin tetrachloride (SnCl 4), titanium tetrachloride (TiCl 4), boron trifluoride (BF 3), manganese tetrachloride (MnCl 4), molybdenum pentachloride (MoCl 5), alchlor (AlBr 3), dibrominated magnesium (MgBr 2), zinc powder (Zn), oxide powder and zinc (ZnO), graphite (C), sulfuric acid (H 2SO 4), phosphoric acid (H 3PO 4), polyphosphoric acid (H N+2P nO 3n+1, n is an integer), in the hydrogen fluoride one or more.
The said quaternizing agent of step (5) is a kind of in the following tertiary amine:
(1) trialkylamine, general structure does
Figure G2009101077071D00041
Wherein, R 1, R 2And R 3Be hydrogen, methyl, ethyl, propyl group or butyl;
(2) imidazoles, general structure does
Figure G2009101077071D00042
R wherein 1, R 2, R 3And R 4Be hydrogen, methyl, ethyl, propyl group, butyl, amyl group, octyl group or phenyl;
(3) pyridine, general structure does
Figure G2009101077071D00051
R wherein 1, R 2, R 3, R 4And R 5Be hydrogen, methyl, ethyl or phenyl;
(4) benzoglyoxaline, general structure does R wherein 1Be hydrogen, methyl, ethyl, propyl group, butyl, amyl group or octyl group;
(5) pyrroles, general structure does
Figure G2009101077071D00053
R wherein 1, R 2And R 3Be hydrogen, methyl, ethyl, propyl group, butyl or ethanoyl;
(6) pyrazoles, general structure does
Figure G2009101077071D00054
R wherein 1, R 2And R 3Be hydrogen, methyl, ethyl, propyl group, butyl, amyl group, octyl group or phenyl;
(7) pyrroline comprises: the 1-pyrroline, structural formula does
Figure G2009101077071D00055
R wherein 1Be hydrogen or methyl and 3-pyrroline, structural formula does
Figure G2009101077071D00056
R wherein 1Be hydrogen or benzyl;
(8) quinoline, structural formula does R wherein 1, R 2Be hydrogen, methyl, ethyl, propyl group or butyl, or isoquinoline 99.9, structural formula does
Figure G2009101077071D00062
R wherein 1, R 2Be hydrogen, methyl, ethyl, propyl group or butyl;
(9) triazole, structural formula does
Figure G2009101077071D00063
R wherein 1Be hydrogen or methyl;
(10) dipyridyl; Comprise 2; 2 '-dipyridyl; Structural formula is and 4; 4 '-dipyridyl, structural formula is
Figure G2009101077071D00065
More specifically, wherein, the concentration of polystyrene solution is 0.1～1M in the step (1); Organic solvent is preferably from trichloromethane, methylene dichloride, 1, one or more mixing in 2-ethylene dichloride, the sym.-tetrachloroethane;
The add-on of middle chloromethylation reagent of step (2) or chloroacetylation reagent is preferably 0.1-1 times of PS mole number;
Lewis acid catalyst is aluminum chloride, iron trichloride or zinc dichloride in the step (3), and add-on is step (2) institute's chlorination methylating reagent or chloroacetylation reagent mole number 1～2 times; Reaction times is 6～24 hours.
Quaternizing agent is pyridine, imidazoles or trialkylamine in the step (5).Preferred self-structure formula is the pyridine of
Figure G2009101077071D00071
; The N-Methylimidazole; Structural formula is
Figure G2009101077071D00072
or Trimethylamine 99, and structural formula is
Figure G2009101077071D00073
Embodiment 1
1. chloromethylation: get the there-necked flask that 1.02g (0.01mol) PS is put into 250ml, add the 30ml methylene dichloride and make solvent, at room temperature stir about is 20 minutes, and PS is fully dissolved; Dropwise drip 1 then, 4-dichloro methyl butyl ether adds 0.5g (0.0036mol) zinc dichloride again; At room temperature reacted 20 hours, product is poured in the 40ml 1M hydrochloric acid soln, fully stir; Add 100ml ethanol product is separated out, respectively wash 2 times, used distilled water immersion again 12 hours with distillation washing and ethanol; Suction filtration, 60 ℃ of oven dry, 40 ℃ of vacuum held 24 hours, white cotton-shaped chloromethylated polystyrene product. 1H-NMR nuclear-magnetism spectrum confirms that chloroacetylation PS product structure formula is:
The chloromethyl molar content is 42% in the product.
2. quaternized: as to get the single port flask that 1.2g step 1 gained chloromethylated polystyrene is put into 150ml, add the 30ml DMSO 99.8MIN. and make solvent, stir and treat that the chloroacetylation PS dissolves fully; Add the 10ml pyridine; Stirring reaction is 48 hours under room temperature, then reaction solution is poured in the watch-glass, in 60 ℃ of vacuum-dryings 2 days; Scrape membranaceous residue and place beaker; With deionized water washing by soaking 10 times repeatedly,, again the residue film was promptly got product in 12 hours 60 ℃ of vacuum-dryings to remove dimethyl sulfoxide solvent and unreacted pyridine.
1H-NMR nuclear-magnetism spectrum confirms that the product structure formula is:
Recording the maximum methanol absorbed dose in the time of 25 ℃ is 249.3 gram/grams.
Embodiment 2
1. chloromethylation: identical with step 1 among the embodiment 1.
2. quaternized: as to get the single port flask that 1.2g step 1 gained chloromethylated polystyrene is put into 150ml, add the 30ml DMSO 99.8MIN. and make solvent, stir and treat that the chloroacetylation PS dissolves fully; Add 10ml N-Methylimidazole; Stirring reaction is 48 hours under room temperature, then reaction solution is poured in the watch-glass, in 60 ℃ of vacuum-dryings 2 days; Scrape membranaceous residue and place beaker; With deionized water washing by soaking 10 times repeatedly,, again the residue film was promptly got product in 12 hours 60 ℃ of vacuum-dryings to remove dimethyl sulfoxide solvent and unreacted N-Methylimidazole. 1H-NMR nuclear-magnetism spectrum confirms that the product structure formula is:
Figure G2009101077071D00091
Recording the maximum methanol absorbed dose in the time of 25 ℃ is 179.0 gram/grams.
Embodiment 3
1. chloroacetylation: get the there-necked flask that 5.2g (0.04mol) PS is put into 250ml, add 80ml chloroform give solvent, at room temperature stir about is 20 minutes; PS is fully dissolved, dropwise drip 2ml (0.0125mol) chloroacetyl chloride then, add 2.67g (0.02mol) aluminum chloride again; At room temperature stirring reaction is 5 hours, product is poured in the hydrochloric acid soln of 40ml 1M, fully stirs; Add 100ml ethanol product is separated out, respectively wash 2 times, (volume ratio) zero(ppm) water/alcohol immersion of using 1: 1 again 12 hours with distillation washing and ethanol; Suction filtration, 60 ℃ of oven dry were placed 24 hours in 40 ℃ of vacuum, got white cotton-shaped chloroacetylation PS product. 1H-NMR nuclear-magnetism spectrum confirms that chloroacetylation PS product structure formula is:
Figure G2009101077071D00092
The chloracetyl molar content is 25% in the product.
2. quaternized: as to get the single port flask that 1.3g step 1 gained chloroacetylation PS is put into 150ml, add the 30ml DMSO 99.8MIN. and make solvent, stir and treat that the chloroacetylation PS dissolves fully; Add the 10ml pyridine; Stirring reaction is 48 hours under room temperature, then reaction solution is poured in the watch-glass, in 60 ℃ of vacuum-dryings 2 days; Scrape membranaceous residue and place beaker; With deionized water washing by soaking 10 times repeatedly,, again the residue film was promptly got product in 12 hours 60 ℃ of vacuum-dryings to remove dimethyl sulfoxide solvent and unreacted pyridine.
1H-NMR nuclear-magnetism spectrum confirms that the product structure formula is:
Figure G2009101077071D00101
Recording the maximum methanol absorbed dose in the time of 25 ℃ is 50.0 gram/grams.
Embodiment 4
1. chloroacetylation: identical with step 1 among the embodiment 3.
2. quaternized: as to get the single port flask that 1.3g step 1 gained chloroacetylation PS is put into 150ml, add the 30ml DMSO 99.8MIN. and make solvent, stir and treat that the chloroacetylation PS dissolves fully; Add 10ml N-Methylimidazole; Stirring reaction is 48 hours under room temperature, then reaction solution is poured in the watch-glass, in 60 ℃ of vacuum-dryings 2 days; Scrape membranaceous residue and place beaker; With deionized water washing by soaking 10 times repeatedly,, again the residue film was promptly got product in 12 hours 60 ℃ of vacuum-dryings to remove dimethyl sulfoxide solvent and unreacted N-Methylimidazole. 1H-NMR nuclear-magnetism spectrum confirms that the product structure formula is:
Recording the maximum methanol absorbed dose in the time of 25 ℃ is 32.3 gram/grams.
Embodiment 5
1. chloromethylation: get the there-necked flask that 1.02g (0.01mol) PS is put into 250ml, add the 30ml methylene dichloride and make solvent, at room temperature stir about is 20 minutes; PS is fully dissolved, add the 0.6g Paraformaldehyde 96 then, 2ml 36% concentrated hydrochloric acid; Reacted 20 hours down at 50 ℃, add 100ml ethanol product is separated out, respectively wash 2 times with distillation washing and ethanol; Used distilled water immersion again 12 hours; Suction filtration, 60 ℃ of oven dry, 40 ℃ of vacuum held 24 hours, white cotton-shaped chloromethylated polystyrene product. 1H-NMR nuclear-magnetism spectrum confirms that chloroacetylation PS product structure formula is:
The chloromethyl molar content is 63% in the product.
2. quaternized: identical with embodiment 1 quaternized step.Recording the maximum methanol absorbed dose in the time of 25 ℃ is 210.1 gram/grams.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1.一种甲醇吸收剂聚合物的制备方法，其特征在于，以聚苯乙烯为原料，通过氯甲基化反应或者氯乙酰化反应，在苯环上接上含氯甲基或氯乙酰基团，然后通过季铵化反应，制备成聚苯乙烯胺基树脂，该方法包括以下步骤： 1. A preparation method for methanol absorbent polymer, characterized in that, taking polystyrene as raw material, through chloromethylation reaction or chloroacetylation reaction, connecting chloromethyl or chloroacetyl group on benzene ring Group, then by quaternization reaction, be prepared into polystyrene amine base resin, this method comprises the following steps: (1)取聚苯乙烯，将其溶解制成聚苯乙烯溶液； (1) Get polystyrene, dissolve it and make polystyrene solution; (2)向步骤(1)所得聚苯乙烯溶液中加入氯甲基化试剂或者氯乙酰化试剂，加入量不小于溶液中聚苯乙烯摩尔数的0.05倍；其中，所述的氯甲基化试剂为浓度大于12M的浓盐酸与聚合度为8～100的多聚甲醛的混合物或三甲基氯硅烷与聚合度为8～100的多聚甲醛的混合物； (2) Add chloromethylation reagent or chloroacetylation reagent to the polystyrene solution obtained in step (1), and the addition amount is not less than 0.05 times of the molar number of polystyrene in the solution; wherein, the chloromethylation The reagent is a mixture of concentrated hydrochloric acid with a concentration greater than 12M and paraformaldehyde with a degree of polymerization of 8-100 or a mixture of trimethylchlorosilane and paraformaldehyde with a degree of polymerization of 8-100; (3)向步骤(2)所得溶液中加入路易斯酸催化剂，加入量为步骤(2)所加氯甲基化试剂或者氯乙酰化摩尔数的1～6倍，混合均匀进行反应，所述反应在降温条件下进行，温度为-10～60℃，反应时间为0.5～18小时； (3) Add a Lewis acid catalyst to the solution obtained in step (2), in an amount of 1 to 6 times the number of moles of chloromethylation reagent or chloroacetylation added in step (2), mix evenly and react, the reaction Carried out under cooling conditions, the temperature is -10 to 60°C, and the reaction time is 0.5 to 18 hours; (4)将步骤(3)所得反应液倒入盐酸溶液中，混合均匀后，加入乙醇析出产物，盐酸溶液浓度为0.05～5M； (4) Pour the reaction solution obtained in step (3) into the hydrochloric acid solution, after mixing evenly, add ethanol to precipitate the product, and the concentration of the hydrochloric acid solution is 0.05～5M; (5)将步骤(4)所得析出物在季铵化试剂或其溶液中浸泡后干燥，去除多余未反应季铵化试剂或季铵化试剂溶液得聚苯乙烯胺基树脂；季铵化试剂为下列三级胺中的一种： (5) soak the precipitate obtained in step (4) in the quaternizing agent or its solution and then dry it, remove excess unreacted quaternizing agent or quaternizing agent solution to obtain polystyrene amine-based resin; quaternizing agent One of the following tertiary amines: (1)咪唑，结构通式为 
Figure FSB00000750885300011
其中R1、R2、R3和R4为氢、甲基、乙基、丙基、丁基、戊基、辛基或苯基；  (1) imidazole, the general structural formula is
Figure FSB00000750885300011
Wherein R 1 , R 2 , R 3 and R 4 are hydrogen, methyl, ethyl, propyl, butyl, pentyl, octyl or phenyl; (2)吡啶，结构通式为 
Figure FSB00000750885300021
其中R1、R2、R3、R4和R5为氢、甲基、乙基或苯基； (2) pyridine, the general structural formula is
Figure FSB00000750885300021
Wherein R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen, methyl, ethyl or phenyl; (3)苯并咪唑，结构通式为 
Figure FSB00000750885300022
其中R1为氢、甲基、乙基、丙基、丁基、戊基或辛基； (3) benzimidazole, the general structural formula is
Figure FSB00000750885300022
Wherein R is hydrogen, methyl, ethyl, propyl, butyl, pentyl or octyl; (4)吡咯，结构通式为 
Figure FSB00000750885300023
其中R1、R2和R3为氢、甲基、乙基、丙基、丁基或乙酰基； (4) pyrrole, the general structural formula is
Figure FSB00000750885300023
Wherein R 1 , R 2 and R 3 are hydrogen, methyl, ethyl, propyl, butyl or acetyl; (5)吡唑，结构通式为 
Figure FSB00000750885300024
其中R1、R2和R3为氢、甲基、乙基、丙基、丁基、戊基、辛基或苯基； (5) pyrazole, the general structural formula is
Figure FSB00000750885300024
Wherein R 1 , R 2 and R 3 are hydrogen, methyl, ethyl, propyl, butyl, pentyl, octyl or phenyl; (6)1-吡咯啉，结构式为 其中R1为氢或甲基，或3-吡咯啉，结构式为 
Figure FSB00000750885300026
其中R1为氢或苄基；  (6) 1-pyrroline, the structural formula is Where R is hydrogen or methyl, or 3-pyrroline, the structural formula is
Figure FSB00000750885300026
Wherein R is hydrogen or benzyl; (7)喹啉，结构式为 其中R1、R2为氢或甲基，或异喹啉，结构式为 
Figure FSB00000750885300032
其中R1、R2为氢或甲基； (7) Quinoline, the structural formula is Wherein R 1 and R 2 are hydrogen or methyl, or isoquinoline, and the structural formula is
Figure FSB00000750885300032
Wherein R 1 and R 2 are hydrogen or methyl; (8)三氮唑，结构式为 
Figure FSB00000750885300033
其中R1为氢或甲基； (8) triazole, the structural formula is
Figure FSB00000750885300033
Wherein R 1 is hydrogen or methyl; (9)2，2′-联吡啶，结构式为 
Figure FSB00000750885300034
或4，4′-联吡啶，结构式为 
Figure FSB00000750885300035
(9) 2,2'-bipyridine, the structural formula is
Figure FSB00000750885300034
Or 4,4'-bipyridine, the structural formula is
Figure FSB00000750885300035
 2.如权利要求1所述聚合物的制备方法，其中，步骤(4)之后步骤(5)之前，所得析出物先行过滤，滤出物分别用蒸馏水和乙醇进行清洗，再用蒸馏水和乙醇混合液浸泡至少1小时，抽滤后40～60℃真空干燥至少1小时。 2. the preparation method of polymer as claimed in claim 1, wherein, before step (5) after step (4), gained precipitate is filtered earlier, and filtrate cleans with distilled water and ethanol respectively, then mixes with distilled water and ethanol Soak in liquid for at least 1 hour, vacuum dry at 40-60°C for at least 1 hour after suction filtration. 3.如权利要求1所述聚合物的制备方法，其中，在加入乙醇析出产物后，进一步用蒸馏水和乙醇洗产物，所述蒸馏水和乙醇混合液体积比为1∶5～5∶1。 3. The preparation method of the polymer as claimed in claim 1, wherein, after adding ethanol to precipitate the product, the product is further washed with distilled water and ethanol, and the volume ratio of the distilled water and ethanol mixture is 1:5˜5:1. 4.如权利要求1所述聚合物的制备方法，其中，步骤(5)中，将步骤(4)所得产物在季铵化试剂或其溶液中浸泡至少6小时，取出后真空干燥至少12小时，再用去离子水或有机溶剂浸泡洗涤，然后40～60℃再真空干燥至少1小 时。 4. The preparation method of polymer as claimed in claim 1, wherein, in step (5), the product obtained in step (4) is soaked in quaternizing agent or its solution for at least 6 hours, vacuum-dried for at least 12 hours after taking out , then soak and wash with deionized water or organic solvent, and then vacuum dry at 40-60°C for at least 1 hour. 5.如权利要求4所述聚合物的制备方法，其中，所述有机溶剂为甲醇、乙醇、异丙醇、丙酮、乙醚中的一种或几种的混合。 5. the preparation method of polymer as claimed in claim 4, wherein, described organic solvent is the mixing of one or more in methanol, ethanol, Virahol, acetone, ether. 6.如权利要求1所述聚合物的制备方法，其中，步骤(1)中聚苯乙烯选自平均分子量为1000～1,000,000的聚苯乙烯。 6. The preparation method of the polymer according to claim 1, wherein, in the step (1), the polystyrene is selected from polystyrenes with an average molecular weight of 1000-1,000,000. 7.如权利要求1～6任一项所述聚合物的制备方法，其中，步骤(1)中聚苯乙烯溶液的溶剂选自三氯甲烷、二氯甲烷、1，2-二氯乙烷、1，1，2，2-四氯乙烷、二硫化碳、石油醚、硝基苯、N-甲基吡咯烷酮、二甲基亚砜，N，N-二甲基甲酰胺，N，N-二甲基乙酰胺中的一种或几种的混合； 7. the preparation method of polymer as described in any one of claim 1～6, wherein, the solvent of polystyrene solution is selected from chloroform, methylene dichloride, 1,2-ethylene dichloride in step (1) , 1,1,2,2-tetrachloroethane, carbon disulfide, petroleum ether, nitrobenzene, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-di One or more mixtures of methylacetamide; 步骤(3)所述的路易斯酸催化剂为三氯化铝、二氯化锌、三氯化铁、四氯化锡、四氯化钛、三氟化硼、四氯化锰、五氯化钼、三溴化铝、二溴化镁、锌、氧化锌、石墨、硫酸、磷酸、多聚磷酸、氟化氢中的一种或几种，其中，多聚磷酸结构式为Hn+2·Pn·O3n+1，其中，n为整数。 The Lewis acid catalyst described in step (3) is aluminum trichloride, zinc dichloride, iron trichloride, tin tetrachloride, titanium tetrachloride, boron trifluoride, manganese tetrachloride, molybdenum pentachloride , aluminum tribromide, magnesium dibromide, zinc, zinc oxide, graphite, sulfuric acid, phosphoric acid, polyphosphoric acid, hydrogen fluoride, wherein the structural formula of polyphosphoric acid is H n+2 ·P n · O 3n+1 , wherein, n is an integer. 8.如权利要求7所述聚合物的制备方法，其中，步骤(2)所述的氯甲基化试剂为1，1-二氯甲醚，氯甲基甲醚、氯甲基乙醚、氯甲基丙醚、氯甲基辛基醚、1，4-二氯甲氧基丁烷中的一种或几种的混合。 8. the preparation method of polymer as claimed in claim 7, wherein, the chloromethylation reagent described in step (2) is 1,1-dichloromethyl ether, chloromethyl methyl ether, chloromethyl ether, chlorine One or more of methyl propyl ether, chloromethyl octyl ether, and 1,4-dichloromethoxybutane. 9.如权利要求7所述聚合物的制备方法，其中，步骤(1)中聚苯乙烯溶液的浓度为0.1～1M；有机溶剂选自三氯甲烷、二氯甲烷、1，2-二氯乙烷、1，1，2，2-四氯乙烷中一种或几种的混合； 9. The preparation method of polymer as claimed in claim 7, wherein, the concentration of polystyrene solution is 0.1～1M in the step (1); Organic solvent is selected from chloroform, dichloromethane, 1,2-dichloro One or more mixtures of ethane and 1,1,2,2-tetrachloroethane; 步骤(2)中氯甲基化试剂或者氯乙酰化试剂的加入量为聚苯乙烯摩尔数的0.1-1倍； The addition amount of chloromethylation reagent or chloroacetylation reagent in step (2) is 0.1-1 times of polystyrene molar number; 步骤(3)中路易斯酸催化剂为三氯化铝、三氯化铁或二氯化锌，加入量为步骤(2)所加氯甲基化试剂或者氯乙酰化试剂摩尔数的1～2倍；反应时间为6～24小时; In step (3), the Lewis acid catalyst is aluminum trichloride, ferric chloride or zinc dichloride, and the amount added is 1 to 2 times the molar number of chloromethylation reagent or chloroacetylation reagent added in step (2) ; The reaction time is 6 to 24 hours; 步骤(5)中季铵化试剂为吡啶或咪唑。 In step (5), the quaternizing agent is pyridine or imidazole. 10.如权利要求9所述聚合物的制备方法，其中，步骤(5)中季铵化试剂 选自结构式为 的吡啶或N-甲基咪唑，结构式为  10. the preparation method of polymkeric substance as claimed in claim 9, wherein, in step (5), quaternization reagent is selected from structural formula: Pyridine or N-methylimidazole, the structural formula is
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