CN106832340A - A kind of magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof - Google Patents

A kind of magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof Download PDF

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Publication number
CN106832340A
CN106832340A CN201610988993.7A CN201610988993A CN106832340A CN 106832340 A CN106832340 A CN 106832340A CN 201610988993 A CN201610988993 A CN 201610988993A CN 106832340 A CN106832340 A CN 106832340A
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attapulgite
nano
shitosan
solution
plural gel
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张志军
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ANHUI BOSHUO TECHNOLOGY Co Ltd
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ANHUI BOSHUO TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • 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
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives

Abstract

The invention discloses a kind of magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof, it is characterised in that be made up of the raw material of following weight portion：Nano ferriferrous oxide 23, attapulgite 5 10, ethylene glycol 23, hydrochloric acid solution 15 20, solution of zinc sulfate 30 40, appropriate absolute ethyl alcohol, sodium citrate 12, silane coupler KH 570 25, silane coupler KH 550 25, shitosan 23, cerous nitrate 0.4 1, acrylic acid 5 10, appropriate nitrogen distills appropriate amount of water；The present invention coordinates the shitosan for adding to be rich in amino, can not only provide amino and be grafted on attapulgite, participates in crosslinking, strengthens the stability of its network structure, while shitosan has good adsorptivity, can increase the attached amount of load of carrier；Cooperation with the addition of nano ferriferrous oxide, plural gel is had good superparamagnetism.

Description

A kind of magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof
Technical field
The present invention relates to a kind of attapulgite carrier and its preparation, more particularly to a kind of magnetic attapulgite/polyacrylic acid Nano-composite gel and preparation method thereof.
Background technology
Pharmaceutical carrier discharges and targeted system can reduce drug degradation and loss, reduces side effect, improves biological utilisation Degree, thus its research is increasingly taken seriously.High molecular surfactant is due to the amphipathic structure of its uniqueness, Ke Yijin Row self assembly, forms various forms of aggregations, such as micella, microemulsion, gel, liquid crystal, vesica.These aggregations have bag The ability of drug molecule is carried, while have good permeability to film again, the important research field as pharmaceutical carrier.Attapulgite It is a kind of with attapulgite as key component, the ore deposit of zeopan containing Shuifu County with specialty fibers shape Crystal structural morphology Thing.Due to its excellent adsorptivity, ion exchange, rheological characteristic, catalytic and plasticity, and it is applied to prepare pharmaceutical carrier.
Zhu Longxiang is in its master thesis《In-situ polymerization prepares the gel in concave convex rod/polymer nanocomposites Phenomenon and application》In, Nanometer composite hydrogel is prepared for using attapulgite and acrylic acid, but it makes as pharmaceutical carrier With also there is a problem that carrying attached amount, antibiotic property, slow release is not good enough.
The content of the invention
Think deeply based on more than, the present invention is intended to provide a kind of carry the attached pharmaceutical carrier that amount is big, antibiotic property is good with nano combined Hydrogel, and preparation method thereof.
The technical problems to be solved by the invention are realized using following technical scheme：
A kind of magnetic attapulgite/polyacrylic acid nano plural gel, it is characterised in that be by the raw material system of following weight portion Into：
Nano ferriferrous oxide 2-3, attapulgite 5-10, ethylene glycol 2-3, hydrochloric acid solution 15-20, solution of zinc sulfate 30-40, nothing Appropriate water-ethanol, sodium citrate 1-2, Silane coupling reagent KH-570 2-5, silane resin acceptor kh-550 2-5, shitosan 2-3, nitre Sour cerium 0.4-1, acrylic acid 5-10, appropriate nitrogen distill appropriate amount of water；
The concentration of hydrochloric acid solution is 2-6mol/L；Solution of zinc sulfate is 0.5-1mol/L.
Described a kind of magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof, it is characterised in that by Following steps are made：
A. attapulgite is toasted into 1-3h at 120-160 DEG C, after removing organic compound therein, is scattered in distilled water, Add hydrochloric acid solution, solution of zinc sulfate to be activated and ion exchange absorption, add ethylene glycol, nano ferriferrous oxide, 30-60min is stirred and soaked, is obtained rich in silicone hydroxyl, and adsorb the concave convex rod nanometer of zinc ion, nano ferriferrous oxide Rod is brilliant；
B. step a gained concave convex rod nano stick crystals are distributed in absolute ethyl alcohol, add Silane coupling reagent KH-570, silane idol Connection agent KH-550, shitosan, sodium citrate, after ultrasonic disperse 1-3h, 60-90 DEG C of backflow 20-26h, with anhydrous after the completion of reaction Ethanol is washed 2-5 times, after drying, obtains carbon-carbon double bond grafting and amino grafting, the concave convex rod nano stick crystal of chitosan graft；
C. step b gained concave convex rod nano stick crystals are distributed in distilled water, after ultrasonic disperse 1-2h, add cerous nitrate, propylene Acid, under the conditions of nitrogen protection, magnetic agitation, 18-25h is reacted in 50-80 DEG C, is washed away unreacted acrylic acid with distilled water and is gathered Acrylic acid, obtains final product the attapulgite/polypropylene composite materials gel of shitosan reinforcement.
A kind of described magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof, it is characterised in that step Drying condition in rapid b at 30-50 DEG C to be vacuum dried 20-26h.
The beneficial effects of the invention are as follows：Attapulgite is processed with hydrochloric acid solution and solution of zinc sulfate so that attapulgite table Face is rich in silicone hydroxyl, is that the graft modification of next step is prepared, while the zinc ion of absorption has sterilized effect, enables carrier Preferably apply in terms of medical treatment；With silane resin acceptor kh-550 and KH-570 it is attapulgite modified after, obtain amino and carbon carbon The attapulgite of double bond grafting；Under the catalytic action of cerous nitrate, acrylic acid is gone back on concave convex rod nano stick crystal surface by oxidation Original reaction triggers polymerization, and polymerisation is then crosslinked with the attapulgite of grafted amino group and carbon-carbon double bond, forms three dimensional network The Nanometer composite hydrogel of network structure；Meanwhile, the shitosan of addition is rich in amino, can not only provide amino and be grafted to concave convex rod On soil, crosslinking is participated in, strengthen the stability of its network structure, while shitosan has good adsorptivity, carrier can be increased The attached amount of load；Cooperation with the addition of nano ferriferrous oxide, plural gel is had good superparamagnetism.
Specific embodiment
With reference to embodiment, specific embodiment of the invention is further described.
Embodiment
A kind of magnetic attapulgite/polyacrylic acid nano plural gel, it is characterised in that be by the raw material of following weight portion It is made：
Nano ferriferrous oxide 3, attapulgite 10, ethylene glycol 3, hydrochloric acid solution 20, solution of zinc sulfate 40, appropriate absolute ethyl alcohol, Sodium citrate 2, Silane coupling reagent KH-570 5, silane resin acceptor kh-550 5, shitosan 3, cerous nitrate 1, acrylic acid 10, nitrogen In right amount, appropriate amount of water is distilled；
The concentration of hydrochloric acid solution is 2-6mol/L；Solution of zinc sulfate is 0.5-1mol/L.
Described a kind of magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof, it is characterised in that by Following steps are made：
A. attapulgite is toasted into 1-3h at 120-160 DEG C, after removing organic compound therein, is scattered in distilled water, Add hydrochloric acid solution, solution of zinc sulfate to be activated and ion exchange absorption, add ethylene glycol, nano ferriferrous oxide, 30-60min is stirred and soaked, is obtained rich in silicone hydroxyl, and adsorb the concave convex rod nanometer of zinc ion, nano ferriferrous oxide Rod is brilliant；
B. step a gained concave convex rod nano stick crystals are distributed in absolute ethyl alcohol, add Silane coupling reagent KH-570, silane idol Connection agent KH-550, shitosan, sodium citrate, after ultrasonic disperse 1-3h, 60-90 DEG C of backflow 20-26h, with anhydrous after the completion of reaction Ethanol is washed 2-5 times, after drying, obtains carbon-carbon double bond grafting and amino grafting, the concave convex rod nano stick crystal of chitosan graft；
C. step b gained concave convex rod nano stick crystals are distributed in distilled water, after ultrasonic disperse 1-2h, add cerous nitrate, propylene Acid, under the conditions of nitrogen protection, magnetic agitation, 18-25h is reacted in 50-80 DEG C, is washed away unreacted acrylic acid with distilled water and is gathered Acrylic acid, obtains final product the attapulgite/polypropylene composite materials gel of shitosan reinforcement.
A kind of described magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof, it is characterised in that step Drying condition in rapid b at 30-50 DEG C to be vacuum dried 20-26h.
Technical parameter of the invention is：When pH value is 7.0, to the adsorbance of the methylene blue solution of 90.0mg/L >= 302.0 mg/g。

Claims (3)

1. a kind of magnetic attapulgite/polyacrylic acid nano plural gel, it is characterised in that be by the raw material system of following weight portion Into：
Nano ferriferrous oxide 2-3, attapulgite 5-10, ethylene glycol 2-3, hydrochloric acid solution 15-20, solution of zinc sulfate 30-40, nothing Appropriate water-ethanol, sodium citrate 1-2, Silane coupling reagent KH-570 2-5, silane resin acceptor kh-550 2-5, shitosan 2-3, nitre Sour cerium 0.4-1, acrylic acid 5-10, appropriate nitrogen distill appropriate amount of water；
The concentration of hydrochloric acid solution is 2-6mol/L；Solution of zinc sulfate is 0.5-1mol/L.
2. a kind of magnetic attapulgite/polyacrylic acid nano plural gel according to claim 1 and preparation method thereof, its It is characterised by, is made up of following steps：
A. attapulgite is toasted into 1-3h at 120-160 DEG C, after removing organic compound therein, is scattered in distilled water, Add hydrochloric acid solution, solution of zinc sulfate to be activated and ion exchange absorption, add ethylene glycol, nano ferriferrous oxide, 30-60min is stirred and soaked, is obtained rich in silicone hydroxyl, and adsorb the concave convex rod nanometer of zinc ion, nano ferriferrous oxide Rod is brilliant；
B. step a gained concave convex rod nano stick crystals are distributed in absolute ethyl alcohol, add Silane coupling reagent KH-570, silane idol Connection agent KH-550, shitosan, sodium citrate, after ultrasonic disperse 1-3h, 60-90 DEG C of backflow 20-26h, with anhydrous after the completion of reaction Ethanol is washed 2-5 times, after drying, obtains carbon-carbon double bond grafting and amino grafting, the concave convex rod nano stick crystal of chitosan graft；
C. step b gained concave convex rod nano stick crystals are distributed in distilled water, after ultrasonic disperse 1-2h, add cerous nitrate, propylene Acid, under the conditions of nitrogen protection, magnetic agitation, 18-25h is reacted in 50-80 DEG C, is washed away unreacted acrylic acid with distilled water and is gathered Acrylic acid, obtains final product the attapulgite/polypropylene composite materials gel of shitosan reinforcement.
3. a kind of magnetic attapulgite/polyacrylic acid nano plural gel according to claim 2 and preparation method thereof, its Be characterised by, the drying condition in step b be 30-50 DEG C at be vacuum dried 20-26h.
CN201610988993.7A 2016-11-10 2016-11-10 A kind of magnetic attapulgite/polyacrylic acid nano plural gel and preparation method thereof Withdrawn CN106832340A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109942904A (en) * 2019-02-28 2019-06-28 淮阴工学院 A kind of attapulgite clay compounded chitosan gel rubber and preparation method thereof
CN117017840A (en) * 2023-09-20 2023-11-10 广东时尚女孩生物科技有限公司 Gel based on long-acting antibacterial function and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102895958A (en) * 2012-10-24 2013-01-30 常州大学 Attapulgite clay based adsorbing material and preparation method thereof
CN106000356A (en) * 2016-06-16 2016-10-12 江苏麦阁吸附剂有限公司 Attapulgite/polyacrylic acid compound heavy metal absorbent and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102895958A (en) * 2012-10-24 2013-01-30 常州大学 Attapulgite clay based adsorbing material and preparation method thereof
CN106000356A (en) * 2016-06-16 2016-10-12 江苏麦阁吸附剂有限公司 Attapulgite/polyacrylic acid compound heavy metal absorbent and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109942904A (en) * 2019-02-28 2019-06-28 淮阴工学院 A kind of attapulgite clay compounded chitosan gel rubber and preparation method thereof
CN117017840A (en) * 2023-09-20 2023-11-10 广东时尚女孩生物科技有限公司 Gel based on long-acting antibacterial function and preparation method thereof
CN117017840B (en) * 2023-09-20 2023-12-15 广东时尚女孩生物科技有限公司 Gel based on long-acting antibacterial function and preparation method thereof

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Application publication date: 20170613