CN100423821C - Method for preparing long-chain unsaturated fatty acid graft modified acetic-acid cellulose filtering material and preparing method - Google Patents
Method for preparing long-chain unsaturated fatty acid graft modified acetic-acid cellulose filtering material and preparing method Download PDFInfo
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- CN100423821C CN100423821C CNB200710036559XA CN200710036559A CN100423821C CN 100423821 C CN100423821 C CN 100423821C CN B200710036559X A CNB200710036559X A CN B200710036559XA CN 200710036559 A CN200710036559 A CN 200710036559A CN 100423821 C CN100423821 C CN 100423821C
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Abstract
This invention relates to a Preparation method of long chain polyunsaturated fatty acid modified cellulose acetate filter Graft, first cellulose acetate CA membrane cut into diamonds, after washing and freeze-drying in the anhydrous ethanol put it into the benzophenone / ethanol photosensitizer solution, and then placed in a UV irradiation facility irradiation, after irradiation CA membrane dried out and submerged some unsaturated fatty acids, again irradiation grafting reaction; then CA membrane dried out in turn washing in the anhydrous ethanol and deionized water until the pH was neutral; the sample after cleaning into freeze-drying Machine dry to get long-chain polyunsaturated fatty acids graft modified cellulose acetate filter. The surface modified CA membrane of this invention has good blood compatibility. Radiation at room temperature in preparation process, it does not introduce any toxic substances, the reaction conditions is easy.
Description
Technical field
That the present invention relates to is a kind of preparation method of preparing long-chain unsaturated fatty acid graft modified acetic-acid cellulose filtering material, cause the performance of preparing long-chain unsaturated fatty acid graft modified acetic-acid cellulose (CA) filter material with ultraviolet irradiation, the cellulose acetate filter material after the modification is expected to be used for directions such as gas separation, liquid filtering, medicine control release.Belong to polymeric material field.
Background technology
Cellulose acetate (CA) is the cellulose organic ester that carries out commodity production in the cellulose derivative the earliest and constantly develop.Now CA be widely used in make spray paint, coating, textile fabric, plastics, cigaratte filter, packaging material, film, artificial kidney and reverse osmosis membrane etc., be should have in the present cellulosic plastics the most a kind of.Because the hydroxyl in the cellulosic molecule is replaced by acetyl group; weakened the active force of hydrogen bond; big intermolecular distance is increased, therefore utilize CA can make hollow-fibre membrane, be used for gas separation, blood filtration etc. with foaming structure with good blood compatibility and biocompatibility.CA also can be used for preparing capsule, to reach the purpose of medicine controlled release.The cellulose family film has good permeability to water, can effectively remove small-molecule substance harmful in the blood such as creatinine, urea etc., and have certain mechanical strength.In addition, because cellulose is natural macromolecular material, be safe basically to human body.The cellulose family film properties is good, and raw material sources are abundant, cheap, therefore use on the development history of film always in occupation of leading position at blood purification.
Compare with artificial synthetic polymer film, cellulose membrane has higher dimensional stability, good processability, and the biodegradable advantage of nontoxic energy.Since successfully developing the CA film with dissymmetrical structure from Loeb and Souriajan, the CA film just is successfully applied to the bio-separation field.As haemodialysis, filtration, infiltration etc.Many researchers prove that the asymmetric pore structure of CA shows good performance in the filtration of blood, are that blood separates with most important a kind of in the film.But the CA film makes blood in instantaneously coagulated phenomenon in the time of in use also can occurring contacting with blood.In order to reduce this effect, need carry out graft modification to its surface.
Long-chain unsaturated fatty acid mainly be divided into polyunsaturated fatty acid (polyunsaturated fatty acids, PUFA) and monounsaturated fatty acids (Monounsaturated fatty acids, MUFA).Polyunsaturated fatty acid be a class to contain more than 2 or 2 two keys and carbon number be 16～22 straight chain fatty acid, they are all over being stored in living nature.The most representative aliphatic acid in the monounsaturated fatty acids---oleic acid is a kind of important natural materials, is widely used in food and the medical industry.Monounsaturated fatty acids is self-evident to health effects, as protection heart, reduction blood sugar, regulating blood lipoid, reduction cholesterol etc.With unsaturated fatty acid graft modified CA filter material, not only can improve its performance, and can not work the mischief human body, have extremely application prospects.
Uv irradiation appts is simple, and floor space is little, invests for a short time, easily reaches industrial production requirement.And uv photo initiated grafting is introduced chemical substance hardly, can be described as a kind of modification mode of cleaning.Whether be applied to matrix surface in advance according to sensitising agent, liquid-phase grafting can be divided into one-step method and two-step method.One-step method is directly sensitising agent, monomer and matrix to be mixed, and carries out irradiation grafting, produce a large amount of homopolymers and cross-linked polymer but this method is normal, and cross-linked polymer will have a negative impact to filter material.Two-step method then is earlier sensitising agent to be mixed with matrix, matrix is taken out to mix with monomer more then and carries out the irradiation grafting reaction.
There is not at present the technology that adopts long-chain unsaturated fatty acid and the graft modification of ultraviolet irradiation two-step method to prepare modification cellulose acetate filter material openly to report as yet.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, propose a kind of preparation method of preparing long-chain unsaturated fatty acid graft modified acetic-acid cellulose filtering material, reaction condition is simple, the filter material performance improvement after the modification, improve blood compatibility, the range of application of expansion filter material.
For realizing this purpose, the present invention adopts long-chain unsaturated fatty acid as grafted monomers, with the reaction of ultraviolet irradiation initiation grafting, adopts two-step method to improve the performance of cellulose acetate filter material.At first the cellulose acetate base material is immersed in the sensitising agent solution, ultraviolet light irradiation under the condition that does not have monomer to exist, generates the surface light initator, then base material is placed monomer solution, ultraviolet light irradiation, the polymerization of surperficial initator initiation grafting.
Method of the present invention comprises following concrete steps:
1, cellulose acetate CA film is cut into square, in absolute ethyl alcohol, washs freeze drying.
2, the CA film is put into the sensitising agent solution of benzophenone/absolute ethyl alcohol, the concentration of benzophenone is 0.1mol/l～1mol/l in the sensitising agent solution, soaks 1 hour.
3, the sensitising agent solution example pond that will adorn the CA film places ultraviolet irradiation device to carry out irradiation, light source distance sample 10～30cm, and exposure time is 5min～30min.
4, the CA film is taken out, dry, immerse in certain long-chain unsaturated fatty acid, place ultraviolet irradiation device to carry out the irradiation grafting reaction once more, exposure time is 5min～120min.
5, the CA film after the grafting is taken out, place absolute ethyl alcohol to clean, use washed with de-ionized water again, be neutral until the pH of washing lotion value.Sample after cleaning places freeze drier dry, weighs.Obtain long-chain unsaturated fatty acid graft modified cellulose acetate filter material.
Among the present invention, long-chain unsaturated fatty acid described in the step 4 is meant carbon atom number greater than 10 and contain the aliphatic acid of one or more pairs of keys, such as undecenoic acid (1 two key of 11 carbon atoms), oleic acid (1 two key of 18 carbon atoms), linoleic acid (2 two keys of 18 carbon atoms), leukotrienes (3 two keys of 18 carbon atoms), arachidonic acid (4 two keys of 20 carbon atoms) etc.
Compared with prior art, the present invention has significant technique effect.The present invention carries out graft modification with long-chain unsaturated fatty acid to cellulose, and the uv irradiation appts of employing is simple, carries out under the normal temperature air, and reaction fast, and is pollution-free; Reaction condition and the step used in the whole process are simple, and reaction reagent is nontoxic, and the filter material blood compatibility after the modification improves, and does not almost have the blood coagulation haemolysis.
Description of drawings
Fig. 1 is the SEM Electronic Speculum figure that the embodiment of the invention 1 adopts oleic acid graft modification CA film front and back.
Among Fig. 1, (a) be the SEM Electronic Speculum figure before the graft modification, (b) be the SEM Electronic Speculum figure after the graft modification.
The specific embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1
The CA film is cut into the square of 8*8, cleans, weigh after the freeze drying with absolute ethyl alcohol.The CA film is put into benzophenone/absolute ethyl alcohol sensitising agent solution, and the concentration of benzophenone is 0.1mol/l in the sensitising agent solution, soaks to be placed on (fluorescent tube is apart from 15cm) in the ultraviolet irradiation device in 1 hour, and irradiation 5min taking-up is dried standby; CA film after will handling with sensitising agent immerses in the oleic acid fully, places ultraviolet irradiation device again, carries out the irradiation grafting reaction; Exposure time is 5min, takes out and is placed on soaking and washing in the absolute ethyl alcohol, uses washed with de-ionized water again, and is alternately saturating clearly until washing lotion with absolute ethyl alcohol and washed with de-ionized water, and it is neutral that its pH value is.Sample after cleaning places freeze drier to be dried to constant weight, weighs, and obtains long-chain unsaturated fatty acid graft modified cellulose acetate filter material.
The excursion that adopts pH meter to measure the acid-base value of washing lotion is 0.5, can confirm that the pH of washing lotion changes the needs (≤1.5) that meet the blood filter material.
Adopt the surface of scanning electron microscopic observation CA film, from Fig. 1 as seen, a figure matrix is ganoid film, and behind the ultraviolet irradiation graft reaction, obvious variation has taken place matrix surface among the b figure, illustrates that oleic acid successfully grafts on the CA surface.
Adopt the weightening finish method to carry out the calculating of percent grafting, CA film weightening finish 1% after the confirmation grafting.
Adopt the haemolysis performance test to weigh the blood compatibility of CA film behind the surface grafting, confirm the no obvious blood coagulation haemolysis in CA film surface after the grafting.
Embodiment 2
The CA film is cut into the square of 8*8, cleans, weigh after the freeze drying with absolute ethyl alcohol.The CA film is put into benzophenone/absolute ethyl alcohol sensitising agent solution, and the concentration of benzophenone is 0.5mol/l in the sensitising agent solution, soaks to be placed on (fluorescent tube is apart from 15cm) in the ultraviolet irradiation device in 1 hour, and irradiation 30min taking-up is dried standby; CA film after will handling with sensitising agent immerses in the oleic acid fully, places ultraviolet irradiation device again, carries out the irradiation grafting reaction; Exposure time is 120min, takes out and is placed on soaking and washing in the absolute ethyl alcohol, uses washed with de-ionized water again, and is alternately saturating clearly until washing lotion with absolute ethyl alcohol and washed with de-ionized water, and it is neutral that its pH value is.Sample after cleaning places freeze drier to be dried to constant weight, weighs, and obtains long-chain unsaturated fatty acid graft modified cellulose acetate filter material.
The excursion that adopts pH meter to measure the acid-base value of washing lotion is 1.0, can confirm that the pH of washing lotion changes the needs (≤1.5) that meet the blood filter material.
Adopt the weightening finish method to carry out the calculating of percent grafting, CA film weightening finish 20% after the confirmation grafting.
Embodiment 3
The CA film is cut into the square of 8*8, cleans, weigh after the freeze drying with absolute ethyl alcohol.The CA film is put into benzophenone/absolute ethyl alcohol sensitising agent solution, and the concentration of benzophenone is 1mol/l in the sensitising agent solution, soaks 1h and is placed on (fluorescent tube is apart from 15cm) in the ultraviolet irradiation device, and irradiation 10min taking-up is dried standby; CA film after will handling with sensitising agent immerses in the undecenoic acid fully, places ultraviolet irradiation device again, carries out the irradiation grafting reaction; Exposure time is 30min, takes out and is placed on soaking and washing in the absolute ethyl alcohol, uses washed with de-ionized water again, and is alternately saturating clearly until washing lotion with absolute ethyl alcohol and washed with de-ionized water, and it is neutral that its pH value is.Sample after cleaning places freeze drier to be dried to constant weight, weighs, and obtains long-chain unsaturated fatty acid graft modified cellulose acetate filter material.
The excursion that adopts pH meter to measure the acid-base value of washing lotion is 0.6, can confirm that the pH of washing lotion changes the needs (≤1.5) that meet the blood filter material.
Adopt the weightening finish method to carry out the calculating of percent grafting, CA film weightening finish 12% after the confirmation grafting.
Embodiment 4
The CA film is cut into the square of 8*8, cleans, weigh after the freeze drying with absolute ethyl alcohol.The CA film is put into benzophenone/absolute ethyl alcohol sensitising agent solution, and the concentration of benzophenone is 0.5mol/l in the sensitising agent solution, soaks 1h and is placed on (fluorescent tube is apart from 15cm) in the ultraviolet irradiation device, and irradiation 10min taking-up is dried standby; CA film after will handling with sensitising agent immerses in the linoleic acid fully, places ultraviolet irradiation device again, carries out the irradiation grafting reaction; Exposure time is 30min, takes out and is placed on soaking and washing in the absolute ethyl alcohol, uses washed with de-ionized water again, and is alternately saturating clearly until washing lotion with absolute ethyl alcohol and washed with de-ionized water, and it is neutral that its pH value is.Sample after cleaning places freeze drier to be dried to constant weight, weighs, and obtains long-chain unsaturated fatty acid graft modified cellulose acetate filter material.
The excursion that adopts pH meter to measure the acid-base value of washing lotion is 0.7, can confirm that the pH of washing lotion changes the needs (≤1.5) that meet the blood filter material.
Adopt the weightening finish method to carry out the calculating of percent grafting, CA film weightening finish 9% after the confirmation grafting.
Claims (2)
1. the preparation method of a preparing long-chain unsaturated fatty acid graft modified acetic-acid cellulose filtering material is characterized in that may further comprise the steps:
1) CAM is cut into square, in absolute ethyl alcohol, washs, freeze drying;
2) CAM is put into the sensitising agent solution of benzophenone/absolute ethyl alcohol, the concentration of benzophenone is 0.1mol/l～1mol/l in the sensitising agent solution, soaks 1 hour;
3) the sensitising agent solution that will adorn CAM after soaking places ultraviolet irradiation device to carry out irradiation, light source distance CAM 10～30cm, and exposure time is 5min～30min;
4) the CAM taking-up is dried, immerse in the long-chain unsaturated fatty acid, place ultraviolet irradiation device to carry out the irradiation grafting reaction once more, exposure time is 5min～120min; Described long-chain unsaturated fatty acid is carbon atom number greater than 10 and contains the aliphatic acid of one or more pairs of keys;
5) CAM after the grafting is taken out, place absolute ethyl alcohol to clean, use washed with de-ionized water again, be neutral until the pH of washing lotion value; The sample after cleaning freeze drying obtains long-chain unsaturated fatty acid graft modified cellulose acetate filter material.
2. according to the preparation method of the preparing long-chain unsaturated fatty acid graft modified acetic-acid cellulose filtering material of claim 1, it is characterized in that described long-chain unsaturated fatty acid is undecenoic acid, oleic acid, linoleic acid, leukotrienes or arachidonic acid.
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| CN101302713B (en) * | 2008-06-12 | 2010-06-09 | 上海交通大学 | Method for preparing phosphoryl choline modified nonwoven cloth for filtering blood |
| CN116020288A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Modified net film, preparation method, application and device and method for treating oily sewage |
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| JPS51140885A (en) * | 1975-05-30 | 1976-12-04 | Sekisui Chem Co Ltd | A process for production of semipermeable film material |
| JP2004081837A (en) * | 2002-06-28 | 2004-03-18 | Hitoshi Kanazawa | Method for improving dentition correcting material and dental care material |
| WO2006082803A1 (en) * | 2005-02-01 | 2006-08-10 | Kyoto University | Fiber-reinforced composite material and process for producing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51140885A (en) * | 1975-05-30 | 1976-12-04 | Sekisui Chem Co Ltd | A process for production of semipermeable film material |
| JP2004081837A (en) * | 2002-06-28 | 2004-03-18 | Hitoshi Kanazawa | Method for improving dentition correcting material and dental care material |
| WO2006082803A1 (en) * | 2005-02-01 | 2006-08-10 | Kyoto University | Fiber-reinforced composite material and process for producing the same |
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| 分离膜用纤维素材料改性研究的进展. 汪勇，程博闻，杜启云.膜科学与技术，第22卷第4期. 2002 |
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Assignee: Suzhou Yitong Filter Technology Co., Ltd. Assignor: Shanghai Jiao Tong University Contract record no.: 2010320000851 Denomination of invention: Method for preparing long-chain unsaturated fatty acid graft modified acetic-acid cellulose filtering material and preparing method Granted publication date: 20081008 License type: Exclusive License Open date: 20070829 Record date: 20100705 |
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