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CN109535316A - A kind of n-isopropyl acrylamide hydridization integral post and preparation method thereof - Google Patents

A kind of n-isopropyl acrylamide hydridization integral post and preparation method thereof Download PDF

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CN109535316A
CN109535316A CN201811354539.1A CN201811354539A CN109535316A CN 109535316 A CN109535316 A CN 109535316A CN 201811354539 A CN201811354539 A CN 201811354539A CN 109535316 A CN109535316 A CN 109535316A
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isopropylacrylamide
capillary
siloxane
preparation
monolithic column
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申钦鹏
段沅杏
李源栋
赵杨
夏建军
赵辉
杨继
刘春波
唐石云
王昆淼
张凤梅
司晓喜
陈应庄
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China Tobacco Yunnan Industrial Co Ltd
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China Tobacco Yunnan Industrial Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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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
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3028—Granulating, agglomerating or aggregating

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Abstract

一种N‑异丙基丙烯酰胺杂化整体柱及其制备方法，包括以下步骤：将毛细管进行预处理使其内壁表面带有烯键；将硅氧烷交联剂、硅氧烷偶联剂、N‑异丙基丙烯酰胺、聚乙二醇、尿素、醋酸水溶液及引发剂混合得到预聚液，其中硅氧烷偶联剂含有烯键和硅氧烷基团，硅氧烷交联剂含有多个聚合结构，聚合结构含有硅氧烷基团；将毛细管置于预聚液中且使预聚液进入毛细管内，并将毛细管的两端密封，交联剂与毛细管的内壁和偶联剂发生烯键聚合反应形成骨架结构，同时偶联剂的烯基和N‑异丙基丙烯酰胺发生开环反应，得到N‑异丙基丙烯酰胺杂化整体柱。本发明的方法制得的N‑异丙基丙烯酰胺杂化整体柱具有疏水性，分离能力强。

An N-isopropylacrylamide hybrid monolithic column and a preparation method thereof, comprising the following steps: pretreating a capillary to make its inner wall surface with ethylenic bonds; , N-isopropylacrylamide, polyethylene glycol, urea, acetic acid aqueous solution and initiator are mixed to obtain a prepolymerization solution, wherein the siloxane coupling agent contains olefinic bonds and siloxane groups, and the siloxane crosslinking agent Contains multiple polymeric structures, and the polymeric structures contain siloxane groups; place the capillary in the prepolymer solution and let the prepolymer solution enter the capillary, seal both ends of the capillary, and couple the crosslinking agent to the inner wall of the capillary. The olefinic polymerization reaction of the agent forms a skeleton structure, and at the same time, the alkenyl of the coupling agent and N-isopropylacrylamide undergo a ring-opening reaction to obtain an N-isopropylacrylamide hybrid monolithic column. The N-isopropylacrylamide hybrid monolithic column prepared by the method of the invention has hydrophobicity and strong separation ability.

Description

A kind of n-isopropyl acrylamide hydridization integral post and preparation method thereof
Technical field
The present invention relates to substance separation technology field, more particularly to a kind of n-isopropyl acrylamide hydridization integral post and Preparation method.
Background technique
In chemical substance separation technology field, as isolated core, chromatographic column plays critical effect.Presently the most Common chromatographic column can be divided into positive and reverse chromatograms two major classes.Wherein the polarity of stationary phase is less than mobile phase in reverse-phase chromatography Polarity, reverse-phase chromatography are widely used in the separation analysis of middle polarity and low pole compound.Divide from stationary phase angle, it can be with It is divided into two class of packed column and integral post, integral post (monolith column) is considered as stationary phase of new generation, it is by list Body, crosslinking agent, pore-foaming agent and initiator mixed solution caused in capillary column by in-situ heat or light initiation polymerization obtains The cylinder with co-continuous porous structure arrived.Integral post has the characteristics that preparation is simple, structure is uniform, permeability is good, thus Obtain very high separative efficiency.
Organic-inorganic hybridization monolithic column reported by Zou Hanfa seminar for the first time, by simultaneously using organic monomer and inorganic Monomer is polymerize, so that obtain integral post and can obtain enough rigidity also and can guarantee to possess enough organo-functional groups, To realize the unification of service life and separating capacity.Sol-gal process is due to being easy to obtain using aqueous polymerization method Biggish specific surface area is obtained, thus is one of the prefered method for being prepared with machine inorganic hybridization integral post, is very suitable to have with preparation There is the preparation of hydrophily hydridization integral post, but the water solubility of hydrophobic monomer limits it in the preparation of hydrophobicity hydridization integral post Application.
Summary of the invention
Based on this, it is necessary to provide a kind of method for preparing hydrophobic hydridization integral post using sol-gal process.
First aspect present invention is related to a kind of preparation method of n-isopropyl acrylamide hydridization integral post, including following step It is rapid:
A, capillary is carried out pretreatment makes its inner wall surface with ethylene linkage functional group；
B, siloxane crosslinker, silicone coupling agents, n-isopropyl acrylamide, urea, polyethylene glycol, acetic acid is water-soluble Liquid and initiator are mixed to get pre-polymerization liquid, wherein the silicone coupling agents contain ethylene linkage and siloxy group, the siloxanes is handed over Connection agent contains paradigmatic structure, and the paradigmatic structure is siloxane group；
C, it will be placed in the pre-polymerization liquid by pretreated capillary and enter the pre-polymerization liquid in the capillary, And by the both ends of the capillary seal, the ethylene linkage of the silicone coupling agents respectively with the ethylene linkage on the inner wall of the capillary Ethylene linkage polymerization reaction occurs for functional group and n-isopropyl acrylamide monomer, realizes that skeleton is fixed and monomer introduces, the silicon oxygen Logical react with siloxane crosslinker generation condensation polymerization of the siloxy group of alkane coupling agent is connected to form skeleton structure, obtains the N- N-isopropylacrylamide hydridization integral post.
The preparation method of n-isopropyl acrylamide hydridization integral post of the present invention, utilizes silicone coupling agents and N- isopropyl Acrylamide free radical polymerization introduces hydrophobic isopropyl, and column bed is formed directly in capillary by crosslinking agent, makes Obtain n-isopropyl acrylamide hydridization integral post.Obtained n-isopropyl acrylamide hydridization integral post hydrophobicity is good, mechanical strong Degree is high, and this method is easy to operate, favorable reproducibility.
In the preparation method of the above n-isopropyl acrylamide hydridization integral post, the pre-polymerization liquid is placed at 0~5 DEG C and is made With 1~4h, so that siloxane group occurs hydrolysis and generates polymerizable silicone hydroxyl.
In the preparation method of the above n-isopropyl acrylamide hydridization integral post, at 30~50 DEG C of the capillary with it is described Pre-polymerization liquid effect 4~for 24 hours, so that the ethylene linkage polymerization reaction and the condensation reaction occur for the pre-polymerization liquid.
In the preparation method of the above n-isopropyl acrylamide hydridization integral post, the weight percent of the pre-polymerization liquid is formed It is as follows: siloxane crosslinker 15~25%, silicone coupling agents 4~10%, n-isopropyl acrylamide 2~5%, urea 5~ 8%, polyethylene glycol 4~9%, aqueous acetic acid 50~65% and initiator 0.05~0.1%.
In the preparation method of the above n-isopropyl acrylamide hydridization integral post, the molecular weight polyethylene glycol is greater than 1000, more optimized molecular weight polyethylene glycol is 2000.
In the preparation method of the above n-isopropyl acrylamide hydridization integral post, the silicone coupling agents are vinyl three Methoxy silane.
In the preparation method of the above n-isopropyl acrylamide hydridization integral post, the siloxane crosslinker is tetramethoxy Silane.
In the preparation method of the above n-isopropyl acrylamide hydridization integral post, step A passes through the side included the following steps Method is implemented:
A1, the inner wall surface that capillary glass tube is successively handled with NAOH solution and hydrochloric acid solution, have its inner wall surface Silicone hydroxyl；Then,
A2, the inner wall surface is handled with bifunctional reagent's 3- methacrylic acid oxygen propyl trimethoxy silicane, wherein Condensation reaction occurs for the silicone hydroxyl on trimethoxy silane group and capillary tube inner wall surface, so that the inner wall surface be made to have Ethylene linkage functional group.
In the preparation method of the above n-isopropyl acrylamide hydridization integral post, the initiator is two NSC 18620 salt of azo Hydrochlorate.
Second aspect of the present invention is related to a kind of n-isopropyl acrylamide hydridization integral post, uses first aspect present invention The preparation method is made.Its hydrophily is strong, high mechanical strength, the favorable reproducibility of product；Furthermore preparation method is simple, ring Guarantor property is good.
Detailed description of the invention
Fig. 1 is the reaction mechanism figure of embodiment；
Fig. 2 is the scanning electron microscope (SEM) photograph for the n-isopropyl acrylamide hydridization entirety column section that embodiment obtains；
Fig. 3 is the column bed material (b) and N- isopropyl third for the n-isopropyl acrylamide hydridization integral post that embodiment obtains The infrared spectrum of acrylamide monomer (a)；
Fig. 4 is the column back pressure for the n-isopropyl acrylamide hydridization integral post that embodiment obtains and the relationship of linear flow rate Figure.
Fig. 5 is benzene compound separation chromatography in the n-isopropyl acrylamide hydridization integral post that embodiment obtains Figure.
Fig. 6 is phenol compound separation chromatography in the n-isopropyl acrylamide hydridization integral post that embodiment obtains Figure.
Fig. 7 is amino benzenes compounds separation chromatography in the n-isopropyl acrylamide hydridization integral post that embodiment obtains Figure.
Fig. 8 is benzoic acid derivative separation chromatography in the n-isopropyl acrylamide hydridization integral post that embodiment obtains Figure.
Fig. 9 is that polycyclic arene compound separates color in the n-isopropyl acrylamide hydridization integral post that embodiment obtains Spectrogram.
Figure 10 is perfluorochemical separation chromatogram in the n-isopropyl acrylamide hydridization integral post that embodiment obtains.
Figure 11 is that chlorophenol species compound separates color in the n-isopropyl acrylamide hydridization integral post that embodiment obtains Spectrogram.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to herein Described embodiment.Purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Step S100: capillary, which is carried out pretreatment, makes its inner wall surface with ethylene linkage functional group.
Step S100 is by introducing bifunctional reagent 3- methacrylic acid oxygen propyl trimethoxy silicane (γ- MAPS).Siloxy group is contained in one end of γ-MAPS, reacts with the silicone hydroxyl of quartz capillary wall, and the other end contains ethylene linkage function Group.
The step of step S100 is specifically included in one of the embodiments: using NaOH solution, water, hydrochloric acid, water and methanol It passes sequentially through capillary and washs 8~14h, drying.γ-MAPS solution is fitted into capillary and seals the both ends of capillary. Capillary equipped with silane mixture liquid is placed in 8~14h of reaction at 60~70 DEG C.It is washed with methanol by capillary, dries up, obtain To by pretreated capillary.
Wherein by capillary tube inner wall after NaOH solution is handled, the inner wall of capillary has silicone hydroxyl.The ethylene linkage of γ-MAPS Activity is higher, is easy to polymerize with free radical and other surfaces derivatization reaction.
Specifically, the concentration of NaOH solution is 1mol/L.Specifically, the concentration of hydrochloric acid is 1mol/L.Specifically, γ- MAPS solution is the mixed solution of the γ-MAPS that volume ratio is 1:1 and methanol.Specifically, drying is nitrogen in step S100 Drying.
Preferably, the capillary equipped with silane mixture liquid is placed at 60 DEG C and reacts 12h.
Step S200: by siloxane crosslinker, silicone coupling agents, n-isopropyl acrylamide, urea, polyethylene glycol, Aqueous acetic acid and initiator mixing, low temperature stirs to get pre-polymerization liquid, wherein the coupling agent contains ethylene linkage and siloxy group, institute It states crosslinking agent and contains paradigmatic structure, the paradigmatic structure is siloxane group；
Preferably, each component ratio is siloxane crosslinker 15~25%, silicone coupling agents 4~10%, N- isopropyl Acrylamide 2~5%, urea 5~8%, polyethylene glycol 4~9%, aqueous acetic acid (0.1M) 50~65% and initiator 0.05 ~0.1%.
Step S300: will be placed in pre-polymerization liquid by pretreated capillary and enter pre-polymerization liquid in capillary, and will The both ends of capillary seal, and ethylene linkage occurs for the silicone hydroxyl and siloxane crosslinker on silicone coupling agents and capillary tube inner wall surface Polymerization reaction forms skeleton structure, while the alkenyl of silicone coupling agents and n-isopropyl acrylamide generation free radical polymerization are anti- It answers, obtains n-isopropyl acrylamide hydridization integral post.
Preferably, will by pretreated capillary at 30~50 DEG C with the pre-polymerization liquid effect 4~for 24 hours so that in advance The ethylene linkage polymerization reaction and the condensation polymerization occur for poly- liquid.It is furthermore preferred that will be by pretreated capillary and pre-polymerization liquid 12h is acted in 40 DEG C to guarantee the abundant progress of ethylene linkage polymerization reaction and condensation polymerization.
It further includes washing step before coming into operation that n-isopropyl acrylamide hydridization integral post is obtained in step S300. Preferably, the condition of washing is successively to pass sequentially through capillary douche with methanol, water, is dried up.The effect of washing is removal capillary Remaining reactant and polynary pore-foaming agent urea, polyethylene glycol and 0.1mol/ aqueous acetic acid, different to obtain porous N- in pipe Propylacrylamide hydridization integral post.
The preparation method of n-isopropyl acrylamide hydridization integral post of the present invention, utilizes silicone coupling agents and N- isopropyl Acrylamide free radical polymerization introduces isopropyl, and column bed is formed directly in capillary by siloxane crosslinker, and N- is made N-isopropylacrylamide hydridization integral post.Obtained n-isopropyl acrylamide hydridization integral post hydrophobicity is good, high mechanical strength, And this method is easy to operate, favorable reproducibility.
The following are specific embodiments.
Capillary is passed sequentially through with the NaOH solution of 1mol/L, water, the hydrochloric acid of 1mol/L, water and methanol and washs 12h, uses nitrogen Air-blowing is dry.γ-MAPS solution γ-the MAPS and methanol of 1:1 (volume ratio be) is fitted into capillary and with silicon rubber by capillary The both ends of pipe seal.Capillary equipped with silane mixture liquid is placed in water-bath 12h at 60 DEG C.It is washed with methanol by capillary 30min is washed, with being dried with nitrogen, is obtained by pretreated capillary.
By PEG100000.175g, urea 0.145g, aqueous acetic acid (0.1M) 1.35mL, 450 μ L of tetramethoxy-silicane, Vinyltrimethoxysilane 150 μ L, n-isopropyl acrylamide 80mg stir hydrolysis after mixing each component and at 0 DEG C 4h is reacted into clear pre-polymerization liquid.
30cm will be cut by pretreated capillary, pre-polymerization liquid will be sucked in capillary；After pre-polymerization liquid fills capillary, The both ends of capillary are used into silicone rubber seal.
Capillary equipped with pre-polymerization liquid is placed in water-bath 12h at 40 DEG C, successively passes sequentially through capillary with water, methanol It rinses, drying obtains n-isopropyl acrylamide hydridization integral post.
Implementation column schematic diagram is as shown in Figure 1.
Structural characterization (1)
Electronic Speculum test is scanned to the section for the n-isopropyl acrylamide hydridization integral post that embodiment obtains, is obtained The scanning electron microscope (SEM) photograph of embodiment is as shown in Figure 2.
The n-isopropyl acrylamide hydridization integral post that embodiment obtains, column bed continuous uniform, and there is porous structure, Illustrate that its permeability is good.
Structural characterization (2)
Column bed material (curve b) and the N- isopropyl third for the n-isopropyl acrylamide hydridization integral post that embodiment is obtained (curve a) carries out Fourier infrared spectrum analysis to acrylamide respectively, obtains infrared spectrum 3, and wherein abscissa is Wavenumber Wave number, unit cm-1, ordinate be Transmittance light transmittance, unit %, as shown in Figure 5.
A and B is compared it is found that wherein in the flexible vibration that 1689cm-1 and 1563cm-1 are respectively carbonyl and N-H in amide groups It is dynamic；Wherein 3290cm-1 is the N-H stretching vibration of Hydrogenbond, and 1387cm-1 and 1367cm-1 are different on N-isopropylacrylamide Symmetrical deformation vibration lotus root on propyl closes division and is formed bimodal.Proof has been successfully introduced into different in the preparation process of integral post Propylacrylamide monomer.
Performance characterization
The mechanical strength of integral post affects its use time and separating effect.Respectively using acetonitrile and water as mobile phase, Column length is the hydridization integral post of 10cm, and using the method for nanoliter liquid chromatogram, it is whole to have investigated n-isopropyl acrylamide hydridization The relationship of the column back pressure (Back-pressure, unit psi) and linear flow rate (Flow rate, unit are μ L/min) of column Figure, as shown in Figure 4.Under test conditions, the column pressure of n-isopropyl acrylamide hydridization integral post is as the increase of flow velocity is in line Property increase, column pressure with tool linear flow rate have good linear relationship (R2> 0.999), show that the n-isopropyl acrylamide is miscellaneous Changing integral post has good mechanical strength and stability.
Separating capacity is to measure the index of the final new energy of integral post, in order to investigate obtained n-isopropyl acrylamide The hydrophilic separating capacity of hydridization integral post, using 95% acetonitrile solution mobile phase the most respectively to ucleosides, phenolic compound, alkali Base class, amides compound have carried out separate evaluation to it.As shown in figures 5-8, respectively alkylbenzene, phenol, phenyl amines, Benzoic acids, multiring aromatic hydrocarbon, perfluorochemical, chlorophenol species separating resulting, the results showed that, four class compounds are in gained entirety Have on column and be effectively maintained ability, and good separation, peak type is symmetrical.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1.一种N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，包括以下步骤：1. a preparation method of N-isopropylacrylamide hybrid monolithic column, is characterized in that, comprises the following steps: A、将毛细管进行预处理使其内壁表面带有烯键官能团；A. The capillary is pretreated to make its inner wall surface with ethylenic functional groups; B、将硅氧烷交联剂、硅氧烷偶联剂、N-异丙基丙烯酰胺、尿素、聚乙二醇、醋酸水溶液及引发剂混合得到预聚液，其中所述硅氧烷偶联剂含有烯键和硅氧烷基，所述硅氧烷交联剂含有聚合结构，所述聚合结构为硅氧烷基团；B. Mix siloxane crosslinking agent, siloxane coupling agent, N-isopropylacrylamide, urea, polyethylene glycol, acetic acid aqueous solution and initiator to obtain a prepolymer solution, wherein the siloxane coupler The linking agent contains an ethylenic bond and a siloxane group, the siloxane crosslinking agent contains a polymeric structure, and the polymeric structure is a siloxane group; C、将经过预处理的毛细管置于所述预聚液中且使所述预聚液进入所述毛细管内，并将所述毛细管的两端密封，所述硅氧烷偶联剂的烯键分别与所述毛细管的内壁上的烯键官能团及N-异丙基丙烯酰胺单体发生烯键聚合反应，实现骨架固定和单体引入，所述硅氧烷偶联剂的硅氧烷基通过与硅氧烷交联剂发生缩合聚合反应相连形成骨架结构，得到所述N-异丙基丙烯酰胺杂化整体柱。C. Place the pretreated capillary in the prepolymer solution and make the prepolymer solution enter the capillary, and seal both ends of the capillary, the olefinic bond of the siloxane coupling agent The ethylenic functional group on the inner wall of the capillary and the N-isopropylacrylamide monomer undergo ethylenic polymerization reaction respectively to realize skeleton fixation and monomer introduction, and the siloxane group of the siloxane coupling agent passes through The N-isopropylacrylamide hybrid monolithic column is obtained by connecting with the siloxane crosslinking agent through condensation polymerization reaction to form a skeleton structure. 2.根据权利要求1所述的N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，将所述预聚液置于0～5℃下作用1～4h，以使硅氧烷基团发生水解生成可聚合硅羟基。2 . The preparation method of N-isopropylacrylamide hybrid monolithic column according to claim 1 , wherein the prepolymerization solution is placed at 0 to 5° C. for 1 to 4 hours, so that the silicon oxygen The alkyl group undergoes hydrolysis to generate polymerizable silanol groups. 3.根据权利要求1所述的N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，将所述经过预处理的毛细管在30～50℃下与所述预聚液作用4～24h，以使所述预聚液发生所述烯键聚合反应及所述缩合聚合反应。3. The preparation method of N-isopropylacrylamide hybrid monolithic column according to claim 1, characterized in that, the pretreated capillary is reacted with the prepolymerization solution at 30-50°C for 4 ~24h, so that the ethylenic polymerization reaction and the condensation polymerization reaction occur in the prepolymerized solution. 4.根据权利要求1所述的N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，所述预聚液的重量百分比组成如下：4. the preparation method of N-isopropylacrylamide hybrid monolithic column according to claim 1, is characterized in that, the weight percent composition of described prepolymerization liquid is as follows: 硅氧烷交联剂15～25％、硅氧烷偶联剂4～10％、N-异丙基丙烯酰胺2～5％、尿素5～8％、聚乙二醇4～9％、醋酸水溶液50～65％及引发剂0.05～0.1％。Siloxane crosslinking agent 15-25%, siloxane coupling agent 4-10%, N-isopropylacrylamide 2-5%, urea 5-8%, polyethylene glycol 4-9%, acetic acid Aqueous solution 50-65% and initiator 0.05-0.1%. 5.根据权利要求1所述的N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，所述硅氧烷交联剂为四甲氧基硅烷。5 . The method for preparing an N-isopropylacrylamide hybrid monolithic column according to claim 1 , wherein the siloxane crosslinking agent is tetramethoxysilane. 6 . 6.根据权利要求1所述的N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，所述硅氧烷偶联剂为乙烯基三甲氧基硅烷。6 . The method for preparing an N-isopropylacrylamide hybrid monolithic column according to claim 1 , wherein the siloxane coupling agent is vinyltrimethoxysilane. 7 . 7.根据权利要求1所述的N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，所述聚乙二醇分子量大于1000。7 . The preparation method of N-isopropylacrylamide hybrid monolithic column according to claim 1 , wherein the molecular weight of the polyethylene glycol is greater than 1000. 8 . 8.根据权利要求1所述的N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，其中步骤A通过包括以下步骤的方法来实施：8. The preparation method of N-isopropylacrylamide hybrid monolithic column according to claim 1, wherein step A is implemented by a method comprising the following steps: A1、用NAOH溶液和盐酸溶液依次处理玻璃毛细管的内壁表面，使其内壁表面带有硅羟基；然后，A1. Treat the inner wall surface of the glass capillary with NaOH solution and hydrochloric acid solution in turn, so that the inner wall surface has silanols; then, A2、用双官能团试剂3-甲基丙烯酸氧丙基三甲氧基硅烷处理所述内壁表面，其中三甲氧基硅烷基团与毛细管内壁表面上的硅羟基发生缩合反应，从而使所述内壁表面带有烯键官能团。A2. Treat the inner wall surface with a bifunctional reagent 3-methacrylate oxypropyltrimethoxysilane, wherein the trimethoxysilane group undergoes condensation reaction with the silanol groups on the inner wall surface of the capillary, so that the inner wall surface has a There are olefinic functional groups. 9.根据权利要求1所述的N-异丙基丙烯酰胺杂化整体柱的制备方法，其特征在于，所述引发剂为偶氮二异丁脒盐酸盐。9 . The preparation method of N-isopropylacrylamide hybrid monolithic column according to claim 1 , wherein the initiator is azobisisobutyramidine hydrochloride. 10 . 10.一种N-异丙基丙烯酰胺杂化整体柱，其特征在于，其根据权利要求1～9任一项所述的N-异丙基丙烯酰胺杂化整体柱的制备方法制备得到。10 . An N-isopropylacrylamide hybrid monolithic column, characterized in that, it is prepared according to the preparation method of an N-isopropylacrylamide hybrid monolithic column according to any one of claims 1 to 9 .
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