Modified macroporous adsorption resin, and preparation method and application thereof

Abstract

The invention relates to a modified macroporous adsorption resin, and a preparation method and application thereof. The preparation method of the modified macroporous adsorption resin comprises the following steps: obtaining macroporous adsorption resin, wherein the surface of the macroporous adsorption resin contains double bonds; and mixing water, an oxidizing agent and the macroporous adsorption resin, and carrying out one-step oxidation reaction to oxidize the double bonds into hydroxyl groups, wherein the oxidizing agent is a combination of sulfuric acid and peracetic acid, or pypocholoride, periodate, or a combination of hydrogen peroxide and peracetic acid, the pypocholoride is at least one of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, and the periodate is at least one of sodium periodate and potassium periodate. According to the preparation method of the modified macroporous adsorption resin, hydrophilic modification of the macroporous adsorption resin can be achieved through one-step reaction, no organic solvent is needed, and the preparation method is environmentally friendly, few in reaction by-products, easy to clean and high in safety to human bodies.

Description

technical field [0001] The invention relates to polymer materials, in particular to a modified macroporous adsorption resin and its preparation method and application. Background technique [0002] As early as 1974, macroporous adsorbent resin was used to adsorb barbiturate and glutamine in blood (see patent document US3794584A). This type of resin is generally synthesized with a high content (>50%) of divinylbenzene as a crosslinking agent, and the specific surface area of ​​the finished product is generally 500-800m 2 / g, on this basis, further by using chloromethyl ether reagents to carry out the Fridel-Crafts (Fridel-Crafts) reaction for secondary cross-linking, the specific surface can be greatly improved, even up to 1000m 2 / g or more (see literature "Wang Jiaxing et al., Preparation and Application of Biochemical Separation Media, Chemical Industry Press, Beijing, P84"). However, since the skeleton structure of the macroporous adsorption resin is prepared by free...

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Problems solved by technology

However, since the skeleton structure of the macroporous adsorption resin is prepared by free radical suspension polymerization of styrene monomer and divinylbenzene, it is highly non-polar and non-selective, and has poor blood compatibility.

[0003] In order to improve the hemocompatibility of macroporous adsorbent resins, the traditional technical routes commonly used are: 1) Prepare ultra-high crosslinked high specific surface adsorbent resins by secondary crosslinking, and deposit polymers with good hemocompatibility on the surface Materials (such as heparin, albumin, xanthan gum, hydroxyethyl cellulose, etc.), but this modification method is physical adsorption, and the deposited envelope material may fall off during clinical application; 2) by The para-position of the benzene ring on the polystyrene unit is substituted by chloromethylation, using chloromethyl as an activation group, grafted with polyethylene glycol (PEG), or grafted with a functional spacer arm (such as 2-ethanolamine). Grafting heparin, choline or serine, or further carboxylation, but this method requires the use of a class of carcinogen chloromethyl ether, the subsequent purification process is complex and will generate a large amount of hazardous waste, and the production cost is high; 3) and hydrophilic Copolymerization of monomers (such as hydroxyethyl methacrylate (HEMA)) to prepare macroporous adsorption resins containing hydrophilic groups, but because the resin production industry is a high-pollution industry, large-scale adsorption resin preparation manufacturers have mature processes, basically no Develop a special production line for the field of blood adsorption, therefore, no related products have been applied; 4) Use the residual double bond on the surface of the macroporous resin to graft hydrophilic monomers (such as HEMA, N-alkylacrylamide, acrylate class), but this method involves secondary initiation of free radical polymerization on the surface of the resin, the reaction process is difficult to control, the chain length of the grafted polymer and the thickness of the grafted layer are uncontrollable, which may affect the macroporous adsorption resin of the matrix. Pore ​​structure parameters, such as pore volume, porosity and pore size etc.; 5) Utilize m-chloroperoxybenzoic acid, hydrogen peroxide or hydrogen peroxide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide ( EDC) complex), sodium hypochlorite, sodium bromide and sulfuric acid complex, hydrogen peroxide plus ultraviolet radiation, organic peroxyacids (such as m-chloroperoxybenzoic acid, peracetic acid, peroxybenzoic acid, trifluoroperacetic acid etc.) and other oxidizing substances to oxidize the remaining double bonds on the surface of the macroporous resin to epoxy groups, or further modify it on this basis, but the modification method is relatively complicated to operate, and a large amount of organic substances harmful to the human body are usually used in the reaction. The solvent is used for swelling, and the by-products produced during the oxidation process of m-chloroperoxybenzoic acid and peroxybenzoic acid, such as m-chlorobenzoic acid and benzoic acid, will also be adsorbed by the resin, which is difficult to clean, and the use of a large number of organic solvents and harmful compounds It will also pollute the environment, resulting in a very complicated post-processing process

And in the oxidation process, there will be a situation where the epoxy group is partially oxidized, and the density of the epoxy group needs to be closely monitored, and the reaction is difficult to quantitatively control

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