CN106581681A - Attapulgite/polyacrylic acid nano composite gel used for medicine carrier and preparation method thereof - Google Patents

Attapulgite/polyacrylic acid nano composite gel used for medicine carrier and preparation method thereof Download PDF

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Publication number
CN106581681A
CN106581681A CN201610988989.0A CN201610988989A CN106581681A CN 106581681 A CN106581681 A CN 106581681A CN 201610988989 A CN201610988989 A CN 201610988989A CN 106581681 A CN106581681 A CN 106581681A
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Prior art keywords
attapulgite
parts
nano
solution
distilled water
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CN201610988989.0A
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Chinese (zh)
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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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Priority to CN201610988989.0A priority Critical patent/CN106581681A/en
Publication of CN106581681A publication Critical patent/CN106581681A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02Inorganic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00Macromolecular compounds obtained by polymerising monomers on to inorganic materials

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses an attapulgite/polyacrylic acid nano composite gel used for a medicine carrier and a preparation method thereof. The nano composite gel is prepared from, by weight, 5-10 parts of attapulgite, 15-20 parts of a hydrochloric acid solution, 30-40 parts of a zinc sulfate solution, a proper amount of anhydrous ethanol, 2-5 parts of a silane coupling agent KH-570, 2-5 parts of a silane coupling agent KH-550, 2-3 parts of chitosan, 0.4-1 part of cerium nitrate, 5-10 parts of acrylic acid, a proper amount of nitrogen gas, and a proper amount of distilled water. The chitosan is rich in amino groups, so that amino groups are supplied for being grafted on the attapulgite and participate in crosslinking, thereby improving the stability of a network structure; in addition, the chitosan has excellent adsorption property, thereby increasing loading quantity of the carrier. The nano composite gel can be applied in the field of medicine carriers better.

Description

A kind of pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel and its preparation Method
Technical field
The present invention relates to a kind of attapulgite carrier and its preparation, more particularly to a kind of pharmaceutical carrier attapulgite/poly- Acrylate/nano pluralgel 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 micelle, microemulsion, gel, liquid crystal, vesicle.These aggregations have bag The ability of drug molecule is carried, while and have good permeability to film, become the important research field of 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 attapulgite/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-releasing 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 problem to be solved is realized using following technical scheme:
A kind of pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel, it is characterised in that be by the original of following weight portion Material is made:
Attapulgite 5-10, hydrochloric acid solution 15-20, solution of zinc sulfate 30-40, appropriate dehydrated alcohol, Silane coupling reagent KH-570 2-5, silane resin acceptor kh-550 2-5, shitosan 2-3, cerous nitrate 0.4-1, acrylic acid 5-10, appropriate nitrogen, distilled water is fitted Amount;
The concentration of hydrochloric acid solution is 2-6mol/L;Solution of zinc sulfate is 0.5-1mol/L.
A kind of pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel according to claim 1 and its system Preparation Method, it is characterised in that be made up of following steps:
A. attapulgite is toasted into 1-3h at 120-160 DEG C, after removing organic compound therein, in being scattered in distilled water, Add hydrochloric acid solution, solution of zinc sulfate to be activated and ion exchange absorption, obtain rich in silicone hydroxyl, and adsorb zinc ion Attapulgite nano stick crystal;
B. step a gained attapulgite nano stick crystal is distributed in dehydrated alcohol, adds Silane coupling reagent KH-570, silane idol Connection agent KH-550, shitosan, after ultrasonic disperse 1-3h, 60-90 DEG C of backflow 20-26h uses absolute ethanol washing 2- after the completion of reaction 5 times, after being dried, obtain carbon-carbon double bond grafting and amino grafting, the attapulgite nano stick crystal of chitosan graft;
C. step b gained attapulgite nano stick crystal is distributed in distilled water, after ultrasonic disperse 1-2h, adds cerous nitrate, propylene Acid, under the conditions of nitrogen protection, magnetic agitation, in 50-80 DEG C 18-25h is reacted, and 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 pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel according to claim 2 and its system Preparation Method, it is characterised in that the drying condition in step b be 30-50 DEG C at be vacuum dried 20-26h.
The invention has the beneficial effects 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 the effect of sterilization, 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 attapulgite nano stick crystal surface by oxidation Original reaction causes polymerization, and polyreaction 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, not only can provide amino and be grafted to attapulgite 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.
Specific embodiment
With reference to embodiment, the specific embodiment of the present invention is further described.
Embodiment
A kind of pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel, it is characterised in that be by following weight portion Raw material make:
Attapulgite 10, hydrochloric acid solution 20, solution of zinc sulfate 40, appropriate dehydrated alcohol, Silane coupling reagent KH-570 5, silane idol Connection agent KH-550 5, shitosan 3, cerous nitrate 1, acrylic acid 10, appropriate nitrogen distills appropriate amount of water;
The concentration of hydrochloric acid solution is 2-6mol/L;Solution of zinc sulfate is 0.5-1mol/L.
A kind of pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel according to claim 1 and its system Preparation Method, it is characterised in that be made up of following steps:
A. attapulgite is toasted into 1-3h at 120-160 DEG C, after removing organic compound therein, in being scattered in distilled water, Add hydrochloric acid solution, solution of zinc sulfate to be activated and ion exchange absorption, obtain rich in silicone hydroxyl, and adsorb zinc ion Attapulgite nano stick crystal;
B. step a gained attapulgite nano stick crystal is distributed in dehydrated alcohol, adds Silane coupling reagent KH-570, silane idol Connection agent KH-550, shitosan, after ultrasonic disperse 1-3h, 60-90 DEG C of backflow 20-26h uses absolute ethanol washing 2- after the completion of reaction 5 times, after being dried, obtain carbon-carbon double bond grafting and amino grafting, the attapulgite nano stick crystal of chitosan graft;
C. step b gained attapulgite nano stick crystal is distributed in distilled water, after ultrasonic disperse 1-2h, adds cerous nitrate, propylene Acid, under the conditions of nitrogen protection, magnetic agitation, in 50-80 DEG C 18-25h is reacted, and 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 pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel according to claim 2 and its system Preparation Method, it is characterised in that the drying condition in step b be 30-50 DEG C at be vacuum dried 20-26h.
The present invention technical parameter be: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 pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel, it is characterised in that be by following weight portion Raw material is made:
Attapulgite 5-10, hydrochloric acid solution 15-20, solution of zinc sulfate 30-40, appropriate dehydrated alcohol, Silane coupling reagent KH-570 2-5, silane resin acceptor kh-550 2-5, shitosan 2-3, cerous nitrate 0.4-1, acrylic acid 5-10, appropriate nitrogen, distilled water is fitted Amount;
The concentration of hydrochloric acid solution is 2-6mol/L;Solution of zinc sulfate is 0.5-1mol/L.
2. a kind of pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel according to claim 1 and its preparation Method, it is characterised in that be made up of following steps:
A. attapulgite is toasted into 1-3h at 120-160 DEG C, after removing organic compound therein, in being scattered in distilled water, Add hydrochloric acid solution, solution of zinc sulfate to be activated and ion exchange absorption, obtain rich in silicone hydroxyl, and adsorb zinc ion Attapulgite nano stick crystal;
B. step a gained attapulgite nano stick crystal is distributed in dehydrated alcohol, adds Silane coupling reagent KH-570, silane idol Connection agent KH-550, shitosan, after ultrasonic disperse 1-3h, 60-90 DEG C of backflow 20-26h uses absolute ethanol washing 2- after the completion of reaction 5 times, after being dried, obtain carbon-carbon double bond grafting and amino grafting, the attapulgite nano stick crystal of chitosan graft;
C. step b gained attapulgite nano stick crystal is distributed in distilled water, after ultrasonic disperse 1-2h, adds cerous nitrate, propylene Acid, under the conditions of nitrogen protection, magnetic agitation, in 50-80 DEG C 18-25h is reacted, and 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 pharmaceutical carrier attapulgite/polyacrylic acid nano pluralgel according to claim 2 and its preparation Method, it is characterised in that the drying condition in step b be 30-50 DEG C at be vacuum dried 20-26h.
CN201610988989.0A 2016-11-10 2016-11-10 Attapulgite/polyacrylic acid nano composite gel used for medicine carrier and preparation method thereof Withdrawn CN106581681A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102114412A (en) * 2011-01-19 2011-07-06 常州大学 Chitosan-grafted and modified attapulgite clay absorbing material and preparation method thereof
CN105708856A (en) * 2016-03-17 2016-06-29 广州格雷特生物科技有限公司 Attapulgite containing pharmaceutical composition for preventing and treating chicken coccidiosis and preparation thereof
CN106006998A (en) * 2016-06-16 2016-10-12 江苏麦阁吸附剂有限公司 Attapulgite/denitrifier composite type wastewater treating agent and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102114412A (en) * 2011-01-19 2011-07-06 常州大学 Chitosan-grafted and modified attapulgite clay absorbing material and preparation method thereof
CN105708856A (en) * 2016-03-17 2016-06-29 广州格雷特生物科技有限公司 Attapulgite containing pharmaceutical composition for preventing and treating chicken coccidiosis and preparation thereof
CN106006998A (en) * 2016-06-16 2016-10-12 江苏麦阁吸附剂有限公司 Attapulgite/denitrifier composite type wastewater treating agent and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱龙祥: "原位聚合制备凹凸棒/聚合物纳米复合材料中的凝胶现象及应用", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

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