The preparation and its application of a kind of porous organic polymer
Technical field
The invention belongs to the preparation of organic high molecular polymer and bio-molecular separation field, and in particular to a kind of poly- DOPA
Amine be modified polystyrene-ethylene glycol dimethacrylate porous organic polymer preparation and in bio-molecular separation field
Application.
Technical background
Porous organic polymer (Porous Organic Polymers, POPs) is a class nonionic, highly cross-linked, tool
There is the general name of the organic high molecular polymer of a large amount of pore structures, be in spy by polymerized monomer, crosslinking agent, pore-foaming agent, dispersant etc.
Aggregated reaction is prepared under fixed condition.After Macroscopic single crystal, pore-foaming agent is removed, will form that aperture is various, shape is each
Hole that is different, interpenetrating, shows as porous three-dimensional network structure, and it is internal with higher porosity in the dry state,
And aperture is larger.Therefore, POPs can be applied to adsorb specific from solution as a kind of organic high molecular polymer adsorbent
The compound of structure, this is a kind of important development in separation analysis field.Because with good absorption property, POPs is
It is widely used in the fields such as industrial decolouring, environmental protection, biological medicine, and increasingly attracts the concern of people.
In order to improve POPs absorption property, it is typically employed in POPs and shows modified method.At present, it is conventional to high score
Sub- polymer particle surface method of modifying has 2 kinds:Physical absorption and chemical bonding.Physical absorption is applied in polymer particle surface
Apply one or more layers polymer containing hydrophilic radical, the hydrophilic granules by a series of post-crosslinking to be stablized simultaneously;
Chemical bonding then often needs first to be bonded active group in polymer particle surface, then recycles its group activity and hydrophily
Polymer is reacted, and hydrophobic purpose is eliminated to reach.The common macromolecule that can be used to be bonded has polyvinyl alcohol, poly- second two
Alcohol, and cyclodextrin etc..
But, for biomolecule, the especially large biological molecule such as polypeptide, protein, polysaccharide, its molecular weight is big, point
Sub- size is big, action site is more, conventional POPs, including modified POPs at present, relative to the absorption property of biomolecule
It is poor.Wherein, most popular is polystyrene-divinylbenzene POPs, but its surface has substantial amounts of phenyl ring and outstanding
Hang double bond, with the defect such as hydrophobicity is small compared with strong, aperture, have a strong impact on its in separation fields such as polypeptide, protein, polysaccharide should
With.
The content of the invention
The present invention provides the preparation method and the application technology in bio-molecular separation field of a kind of porous organic polymer,
I.e. a kind of polystyrene-ethylene glycol dimethacrylate POPs modified using poly-dopamine (PDOPA), the hydrophily of preparation
POPs surfaces have substantial amounts of hydroxyl, can improve its hydrophily and absorption property, while modified POPs possesses stronger machine
Tool intensity, is conducive to improving separating properties of the POPs to biomolecule.
Present invention firstly provides a kind of styrene-ethylene glycol dimethacrylate copolymer, its preparation method is included such as
Under step:
1) by the polyvinyl alcohol high-temperature digestion aqueous phase solution of 0.2~2 mass parts, the table of 0.01~1 mass parts is added
Face activating agent, the electrolyte of 0.01~1 mass parts, the hydroquinones of 0.01~1 mass parts, are mixed and made into continuous phase.
2) by the benzoyl peroxide of 0.1~1 mass parts, the hexadecane of 0.1~1 mass parts, 1~10 mass parts sapn
80th, the styrene of 1~10 mass parts, and the ethylene glycol dimethacrylate of 0.5~10 mass parts are mixed, at ultrasound
Dispersed phase is obtained after reason.
3) by step 1) in continuous phase and step 2) dispersed phase be mixed to join in reaction vessel, held under oxygen-free environment
Filtered after continuous stirring, 5~20h of heating polymerization, the solids being filtrated to get is used successively water, ethanol or methanol, acetone or
After n-hexane washing, styrene-ethylene glycol dimethacrylate copolymer is dried to obtain.
Above-mentioned steps 1) in high temperature be 50~400 DEG C;
Above-mentioned steps 1) in surfactant be lauryl sodium sulfate, dodecyl sodium sulfate, sulfated castor oil
With any of sodium glycocholate or several combinations;
Above-mentioned steps 1) in electrolyte be any of sodium sulphate and sodium carbonate or two kinds combination;
Above-mentioned steps 3) in oxygen-free environment be by be passed through any of nitrogen, argon gas or carbon dioxide or it is several obtain
's;
Above-mentioned steps 3) in mixing speed be 100~400rpm;
Above-mentioned steps 3) in heating-up temperature be 40~200 DEG C.
Another aspect of the present invention provides a kind of porous polymer, is by styrene-ethylene glycol two of 0.01~2 mass parts
Methacrylate copolymer is added in ethanol solution or methanol solution, and the Tris-HCl for adding 20~100 mass parts is molten
Liquid, the Dopamine hydrochloride of 0.01~1 mass parts is well mixed, and adjusts pH value, is carried out after oscillating reactions;Reaction product is carried out
Filtering, be filtrated to get after solids wash with water, ethanol or methanol, acetone or n-hexane successively, dry, i.e., it is obtained of the invention
Porous organic polymer.
Wherein Dopamine hydrochloride is 0.01~1 mass parts;
Wherein pH value is 7~14;
Wherein the reaction time is 1~20h.
Styrene prepared by the present invention-ethylene glycol dimethacrylate copolymer (abbreviation PSEP), available for polypeptide, egg
It is prepared by the separation of the macromolecular compounds such as white matter, polysaccharide.The substantial amounts of hydroxyl in poly-dopamine surface can further derivatization, be prepared into
Meet the separating medium of different demands.Also it can be carried out in SPE chromatogram, size exclusion chromatograph and high performance liquid chromatography field
Wide application.
The porous polymer surface of poly-dopamine modified lithium polystyrene-ethylene glycol dimethacrylate prepared by the present invention
With abundant hydroxyl, fabulous hydrophily and absorption property are shown.Its storage modulus substantially rises, and then shows fabulous
Mechanical strength.The porous polymer of the present invention turns into a kind of equimolecular excellent for separation and Extraction polypeptide, protein, polysaccharide
Material.The porous polymer sheet face of poly-dopamine modified lithium polystyrene-ethylene glycol dimethacrylate has great amount of hydroxy group, can
Carry out amino, hydroxyl, carboxyl, sulfonic group, carbonyl etc., imidazoles, carbazole plasma liquid, polymer brush, poly ion liquid brush, poly- electricity
Solve the functional groups such as matter brush and carry out functionalization, obtain a series of porous polymeric of different specific surface areas, pore volume and average pore size
Thing, enriches the species of the porous material, has widened its application field, with preferable application prospect.
Brief description of the drawings
Fig. 1:The scanning electron microscopic picture of porous organic polymer, wherein a:PSE1;b:D1;c:D2;d:D3.
Fig. 2:The storage modulus figure of porous organic polymer.
Embodiment
The present invention is described in detail with reference to embodiment.
Embodiment 1
The preparation of PSE polymer:Polyvinyl alcohol 0.5g is dissolved in 70mL aqueous phase solutions in 60 DEG C when, dodecane is added
Base sodium sulphate 0.02g, sodium carbonate 0.02g, and hydroquinones 0.015g, mixing, obtain continuous phase, standby;By benzoyl peroxide first
Acyl 0.2g, hexadecane 0.1g, sorbester p17 2g, styrene 2.5g, and ethylene glycol dimethacrylate 1g, mixing, ultrasound
10min, obtains dispersed phase;Continuous phase and dispersed phase are mixed to join in reaction vessel, nitrogen environment, 120rpm is persistently stirred,
65 DEG C of heating polymerization 6h, filtering after the solids being filtrated to get sequentially is washed with water, ethanol and acetone, is dried, that is, benzene is made
Ethene-ethylene glycol dimethacrylate copolymer p SE1.Bovine serum albumin is adsorbed using PSE1, its adsorption capacity is 162mg/
G (in terms of PSE1 dry weights).
Embodiment 2
The preparation of PSE polymer:Polyvinyl alcohol 1.0g is dissolved in 100mL aqueous phase solutions in 100 DEG C when, 12 are added
Sodium alkyl sulfate 0.03g, sodium carbonate 0.04g, and hydroquinones 0.02g, mixing, obtain continuous phase, standby;By benzoyl peroxide first
Acyl 0.3g, hexadecane 0.3g, sorbester p17 3g, styrene 4g, and ethylene glycol dimethacrylate 3g, mixing, ultrasound
30min, obtains dispersed phase;Continuous phase and dispersed phase are mixed to join in reaction vessel, ar gas environment, 200rpm is persistently stirred,
85 DEG C of heating polymerization 8h, filtering after the solids being filtrated to get sequentially is washed with water, methanol and acetone, is dried, that is, benzene is made
Ethene-ethylene glycol dimethacrylate copolymer p SE2.
Weigh obtained PSE2 resin particles 0.2g, add 30% ethanol solution 15mL, Dopamine hydrochloride 0.01g, three
Hydroxymethyl aminomethane (abbreviation Tris) hydrochloric acid solution 20mL, mixing, regulation pH value is oscillating reactions 2h, mistake on 7.5, shaking table
Filter, will be filtrated to get after solids sequentially wash with water, ethanol and n-hexane, drying, i.e., obtained D1 porous organic polymers.
Bovine insulin is adsorbed using D1, its adsorption capacity is 40mg/g (in terms of D1 dry weights).
Embodiment 3
The preparation of PSE polymer:Polyvinyl alcohol 1.5g is dissolved in 200mL aqueous phase solutions in 200 DEG C when, 12 are added
Sodium alkyl sulfate 0.5g, sodium carbonate 0.6g, and hydroquinones 0.4g, mixing, obtain continuous phase, standby;By benzoyl peroxide
0.5g, hexadecane 0.4g, sorbester p17 5g, styrene 6g, and ethylene glycol dimethacrylate 5g, mixing, ultrasonic 60min,
Obtain dispersed phase;Continuous phase and dispersed phase are mixed to join in reaction vessel, carbon dioxide environment, 300rpm is persistently stirred, 100
DEG C heating polymerization 12h, filtering is dry after the solids being filtrated to get sequentially wash with water, methanol and n-hexane, i.e., obtained
Styrene-ethylene glycol dimethacrylate copolymer p SE3.
Obtained PSE3 resin particles 1g is weighed, 60% methanol solution 80mL is added, trishydroxymethylaminomethane is (referred to as
Tris) hydrochloric acid solution 40mL, and Dopamine hydrochloride 0.2g, mixing, regulation pH value is oscillating reactions 10h on 9, shaking table, is filtered,
To be filtrated to get after solids sequentially washs with water, ethanol and acetone, dry, that is, D2 porous organic polymers be made.Utilize
D2 adsorbs bradykinin, and its adsorption capacity is 35mg/g (in terms of D2 dry weights).
Embodiment 4
The preparation of PSE polymer:Polyvinyl alcohol 1.5g is dissolved in 300mL aqueous phase solutions in 300 DEG C when, 12 are added
Sodium alkyl sulfate 0.8g, sodium carbonate 0.9g, and hydroquinones 0.8g, mixing, obtain continuous phase, standby;By benzoyl peroxide
0.7g, hexadecane 0.9g, sorbester p17 8g, styrene 8.5g, and ethylene glycol dimethacrylate 8.9g, mixing, ultrasound
100min, obtains dispersed phase;Continuous phase and dispersed phase are mixed to join in reaction vessel, nitrogen environment, 380rpm is persistently stirred,
150 DEG C of heating polymerization 18h, filtering after the solids being filtrated to get sequentially is washed with water, methanol and acetone, is dried, that is, is made
Styrene-ethylene glycol dimethacrylate copolymer p SE4.
Obtained PSE4 resin particles 1.7g is weighed, 90% ethanol solution 140mL, trishydroxymethylaminomethane is added
(abbreviation Tris) hydrochloric acid solution 90mL, and Dopamine hydrochloride 0.95g, mixing, regulation pH value is oscillating reactions on 10, shaking table
17h, filtering, will be filtrated to get after solids sequentially wash with water, ethanol and n-hexane, drying, i.e., obtained D3 is porous organic
Polymer.Glutathione is adsorbed using D3, its adsorption capacity is 41mg/g (in terms of D3 dry weights).
Characterizing method
1. specific surface area, pore volume and average pore size
The porous organic polymer prepared is determined using BET method, the physical parameter of 7 kinds of polyalcohol stephanoporate particles of the above is as follows
Table:
The physical parameter of the 7 kinds of embodiment polyalcohol stephanoporate particles of the invention of table 1
As known from Table 1, the specific surface area of PSE series plastics, pore volume and average pore size are larger.Therefore, this porous has
Machine polymer is conducive to adsorbing the biomolecule such as protein, the polysaccharide of macromolecular.With the increase of poly-dopamine modification amount, it compares
Surface area, pore volume and average pore size are gradually reduced, and are suitable for separating the less polypeptide of molecular weight.
2. electron microscopic picture
It was found from Fig. 1 scanning electron microscopic picture, PSE1 average pore size is larger, and surface is relatively rough.With poly- DOPA
The increase of amine-modified amount, D1, D2, D3 average pore size is gradually reduced, and surface becomes gradually smooth.
3. mechanical strength
As can be seen from Figure 2, D1, D2, D3 storage modulus gradually increase, and this shows after poly-dopamine modification, its mechanical strength
Increase, and increase with the increase of poly-dopamine modification amount.Therefore, can in porous organic polymer surface modification poly-dopamine
To greatly improve its mechanical strength.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention do not receive above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, it is simple
Change, the displacement that should be equivalent is prevented, is included within protection scope of the present invention.