CN115462384A - DCOIT slow-release nanocapsule taking silicon dioxide as carrier as well as preparation method and application thereof - Google Patents
DCOIT slow-release nanocapsule taking silicon dioxide as carrier as well as preparation method and application thereof Download PDFInfo
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- CN115462384A CN115462384A CN202210921106.XA CN202210921106A CN115462384A CN 115462384 A CN115462384 A CN 115462384A CN 202210921106 A CN202210921106 A CN 202210921106A CN 115462384 A CN115462384 A CN 115462384A
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- dcoit
- release
- nanocapsule
- alkoxy silane
- slow
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- 239000002088 nanocapsule Substances 0.000 title claims abstract description 116
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 49
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 35
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 amino alkoxy silane Chemical compound 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910000077 silane Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008096 xylene Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 37
- 238000013268 sustained release Methods 0.000 claims description 24
- 239000012730 sustained-release form Substances 0.000 claims description 24
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000013265 extended release Methods 0.000 claims description 14
- 239000011162 core material Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005844 autocatalytic reaction Methods 0.000 claims description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001580 bacterial effect Effects 0.000 claims 1
- 230000002538 fungal effect Effects 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 22
- 229940079593 drug Drugs 0.000 abstract description 21
- 238000011068 loading method Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
- 239000003899 bactericide agent Substances 0.000 abstract description 6
- 239000003094 microcapsule Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 9
- 239000007764 o/w emulsion Substances 0.000 description 9
- 238000007605 air drying Methods 0.000 description 7
- 230000005588 protonation Effects 0.000 description 7
- 230000003373 anti-fouling effect Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002519 antifouling agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 244000178870 Lavandula angustifolia Species 0.000 description 2
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000001102 lavandula vera Substances 0.000 description 2
- 235000018219 lavender Nutrition 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229940002612 prodrug Drugs 0.000 description 2
- 239000000651 prodrug Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003487 anti-permeability effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004557 technical material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Dispersion Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a DCOIT slow-release nano capsule taking silicon dioxide as a carrier and a preparation method and application thereof. The preparation method comprises the following steps: under the condition of stirring, dropwise adding amino alkoxy silane into deionized water to obtain an amino alkoxy silane aqueous solution; dissolving DCOIT and alkoxy silane in xylene to obtain a mixed solution; and slowly dripping the mixed solution into the amino alkoxy silane aqueous solution under the stirring condition, reacting under stirring, and separating, washing and drying the obtained reaction solution to obtain the DCOIT slow-release nano capsule taking silicon dioxide as a carrier. The method can improve the embedding rate and the drug loading rate of the nanocapsule and improve the utilization rate of the DCOIT bactericide in the using process; the DCOIT nano-capsule prepared by the invention has regular sphericity, high embedding rate and drug loading rate, can effectively slow down the burst release phenomenon of the drug in the initial use period, and has good DCOIT slow-release effect.
Description
Technical Field
The invention relates to a DCOIT slow-release nano capsule taking silicon dioxide as a carrier, and a preparation method and application thereof, belonging to the technical field of nano capsule preparation.
Background
Marine biofouling presents a serious problem for global marine navigation, marine communications, and the exploitation and utilization of marine resources. Over the years, various antifouling strategies have been implemented to prevent and control biofouling processes, such as mechanical cleaning, electrolysis of seawater, and brushing antifouling paints. Among them, the brush coating of an antifouling paint containing an antifouling agent is the most convenient and most widely used treatment method. Traditional antifouling agents, which typically include organic mercury, toxic lead and cuprous oxide, pose serious threats to the marine environment and human health. Therefore, development of an environment-friendly bactericide and improvement of the utilization rate of the bactericide have been important research subjects in the field of marine antifouling paints.
In the 90 s of the 20 th century, rohm & Haas company, USA, successfully developed a compound with the chemical name 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), and began to market under the registered trademark Sea-Nine 211. DCOIT is white to light yellow powder, not only has the characteristics of low toxicity, long-acting and broad-spectrum sterilization and algae removal, but also has the characteristics of rapid degradation in the environment and small accumulation in organisms. The prize of "preferential Green Chemistry change" and the prize of "chemical environment winning" were obtained in 1996 and 1997 respectively, and are known as environment-friendly bactericides. But similar to other bactericides, the DCOIT is high in content and high in release speed in the initial use stage, and the release concentration is far higher than the effective concentration for inhibiting the attachment of marine fouling organisms; in the later period of use, the content of DCOIT is low, the release speed is slow, and the requirement of inhibiting the biological attachment is difficult to achieve. The microcapsule has the unique advantage of realizing the slow release of the core material, so the DCOIT microcapsule has important significance for fully utilizing DCOIT in the using process and achieving the long-acting antifouling effect.
There are also many documents and patent reports on the preparation of drug-loaded nanocapsules using silica as a carrier. For example, chinese patent document CN108676615A mixes lavender essence with ethyl orthosilicate and silane coupling agent in a reaction kettle to form an oil phase; adding a water phase formed by water and ethanol into the oil phase, adding an emulsifier, and stirring; and adding an alkaline catalyst into the emulsion to react, and obtaining the lavender slow-release essence after the reaction is finished. Chinese patent document CN104548105A discloses a hollow silica microcapsule encapsulated with hydrophobic substance using surfactant micelle solubilized with hydrophobic substance as template and a preparation method thereof. Adding a surfactant into the ethanol solution and uniformly stirring; then adding a mixture of a silicon source and a hydrophobic substance, adding an alkali liquor serving as a catalyst for hydrolytic condensation of the silicon source, adjusting the pH value, and reacting at room temperature; and centrifuging the obtained product, washing with water, and drying at low temperature to obtain the hollow silicon dioxide microcapsule encapsulated with the hydrophobic substance. Such patents, which use different silica precursors and synthesis conditions to prepare silica-supported nanocapsules, can achieve a certain degree of coating of the core material, but have the following problems: (1) The preparation process needs to add extra surfactant and acid or alkali catalyst, the preparation condition is strict, and extra production cost is increased. (2) The steps are carried out in multiple steps, the reaction time is long, and the industrial production of the nano capsules is not easy to carry out. (3) The prepared nano capsule has low encapsulation efficiency and poor encapsulation effect, and cannot control the long-term and stable release of the antifouling agent.
Therefore, the research and development of the preparation method of the DCOIT nano capsule, which has the advantages of simple process, easy realization, low cost, contribution to industrial production, high embedding rate and drug loading and excellent slow-release effect, has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a DCOIT slow-release nano capsule taking silicon dioxide as a carrier and a preparation method and application thereof. The method can improve the embedding rate and the drug loading rate of the nanocapsule and improve the utilization rate of the DCOIT bactericide in the using process; the DCOIT nanocapsule prepared by the invention has regular sphericity and high embedding rate and drug loading rate, can effectively slow down the burst release phenomenon of the drug in the initial period of use, and has good DCOIT slow release effect.
The technical scheme of the invention is as follows:
the DCOIT slow-release nanocapsule takes silicon dioxide as a carrier, and comprises a core material and a wall material; the core material is a xylene solution of DCOIT; the wall material is organic modified silicon dioxide and is formed by the autocatalytic reaction of amino alkoxy silane and alkoxy silane at an oil-water interface.
According to a preferred embodiment of the present invention, the micro-morphology of the nanocapsule is: nanospheres having a particle size of 500-800 nm.
The preparation method of the DCOIT sustained-release nanocapsule taking the silicon dioxide as the carrier comprises the following steps:
(1) Under the condition of stirring, dropwise adding amino alkoxy silane into deionized water to obtain an amino alkoxy silane aqueous solution;
(2) Dissolving DCOIT and alkoxy silane in xylene to obtain a mixed solution; and slowly dripping the mixed solution into the amino alkoxy silane aqueous solution under the stirring condition, reacting under stirring, and separating, washing and drying the obtained reaction solution to obtain the DCOIT slow-release nano capsule taking silicon dioxide as a carrier.
Preferably, in step (1), the aminoalkoxysilane is one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane; preferably, the aminoalkoxysilane is 3-Aminopropyltrimethoxysilane (APS).
Preferably, according to the invention, in steps (1) and (2), the stirring speed is 500-1250rpm.
Preferably, in step (1), the volume ratio of the aminoalkoxysilane to the deionized water is 1.
Preferably, in step (2), the alkoxysilane is one or a combination of two or more of tetraethyl orthosilicate, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, or diethyldiethoxysilane; preferably, the alkoxysilane is methyltrimethoxysilane (MTMS).
Preferably, according to the invention, in step (2), the volume ratio of alkoxysilane to xylene is between 0.2 and 2, preferably between 0.25 and 1.5.
Preferably, according to the invention, in step (2), the ratio between the mass of DCOIT and the volume of xylene is between 0.1 and 0.5 g/mL.
According to the present invention, in the step (2), the volume ratio of the alkoxysilane in the mixed solution to the aminoalkoxysilane in the aqueous solution of the aminoalkoxysilane in the step (1) is preferably 1 to 3.
Preferably, according to the invention, in step (2), the temperature of the reaction is between 15 ℃ and 45 ℃; the reaction time is 6-24h.
Preferably, in step (2), the separation is to separate the nanocapsules by using a centrifuge; the washing is 3-5 times by using water; the drying is carried out at 30-50 ℃ for 12-24h.
Preferably, according to the invention, in step (2), the dropping rate is from 0.5 to 2mL/min.
The application of the DCOIT slow-release nano capsule taking silicon dioxide as a carrier is used as a functional chemical additive for preventing fungi and bacteria from growing; preferably, the nanocapsules are applied as an additive in paints, rubbers, plastics, lubricants or wood.
The invention has the following technical characteristics and beneficial effects:
1. in the process of preparing the silicon dioxide DCOIT slow-release nano capsule, the core material DCOIT is dissolved in dimethylbenzene to be used as an oil phase, so that the content of the core material DCOIT in the oil phase is effectively reducedThe diffusion probability of DCOIT to the water phase improves the embedding rate of the microcapsule. And the invention is distinguished from
The invention utilizes the autocatalytic reaction of amino alkoxy silane and alkoxy silane, preferably methyl trimethoxy silane (MTMS) and 3-aminopropyl trimethoxy silane (APS) on an oil/water interface to encapsulate a core material DCOIT in an organic silicon nanocapsule, and the process does not need additional surfactant and catalyst, and has the advantages of simple preparation process, easy realization of preparation conditions and lower cost.
2. The forming process of the wall material comprises the following steps: (1) When the aminoalkoxysilane is dissolved in water, the amino group will be protonated first, when the positively charged protonated aminoalkoxysilane exhibits amphiphilic properties; (2) When the mixture of alkoxysilane and DCOIT xylene is added drop-wise to the aqueous aminoalkoxysilane solution, the protonated aminoalkoxysilane is dispersed at the oil phase droplet interface; (3) Protonation of the amino group will result in an increase in the pH of the system, providing a basic environment for hydrolysis and condensation of aminoalkoxysilanes and alkoxysilanes at the water-oil interface, where the DCOIT oil droplets act as a spherical soft template; (4) As the reaction time increases, the aminoalkoxysilanes and alkoxysilanes in the oil phase are continuously consumed and the shell thickness continuously increases, thereby forming an organically modified silica wall containing the DCOIT oil phase.
3. In the method, the charging sequence and the charging mode of the amino alkoxy silane and the alkoxy silane are required to be controlled, if the charging sequence is interchanged or the amino alkoxy silane and the alkoxy silane are initially charged into a reaction system together, and the like, the embedding rate and the drug-loading rate of the obtained nano capsule are reduced. In the preparation process of the nanocapsule, the addition amount of the amino alkoxy silane and the alkoxy silane is critical to the embedding rate and the drug loading rate of the obtained nanocapsule, the proportion of the amino alkoxy silane and the alkoxy silane is required to be controlled within the range of the invention, and the embedding rate and the drug loading rate of the obtained microcapsule are reduced due to the fact that the proportion is too high or too low. The amino alkoxy silane and the type of the alkoxy silane also have certain influence on the embedding rate and the drug loading rate of the obtained microcapsule. Namely, the preparation method of the invention as a whole can realize the effect of the invention by the combined action.
4. The silicon dioxide DCOIT slow-release nano capsule prepared by the invention is a white or brown-white powdery uniform sphere, has compact surface and no obvious defect, has the average particle size of 500-800nm, and is easier to be uniformly dispersed in a coating; the silicon dioxide DCOIT nano capsule has the drug embedding rate of 45-55 percent and has better embedding rate and drug-loading rate; the wall material has strong anti-permeability capability and good slow release performance, and can effectively slow down the burst release phenomenon of the medicament in the early stage of use; the silicon dioxide DCOIT nano capsule obtained by the invention has excellent heat resistance and mechanical property of wall materials, and has good thermal stability within 230 ℃.
5. The silicon dioxide DCOIT nano capsule has the advantages of wide raw material source and low price; the silicon dioxide DCOIT nano capsule has simple preparation process and short reaction process, and is beneficial to industrial production; the nano capsule obtained by the invention can be used for marine antifouling coatings, and can also be applied to various industrial fields of rubber, plastic, fiber, lubricating oil, wood industry and the like, so that the application range of the nano capsule is widened.
Drawings
FIG. 1 is an SEM photograph of silica-supported DCOIT extended release nanocapsules prepared in example 1; wherein A is a morphology graph of the nanocapsule aggregate; b is a morphology chart of the ruptured nanocapsules.
Fig. 2 is an infrared spectrum of the DCOIT sustained-release nanocapsule, DCOIT and blank nanocapsule prepared in example 1 using silica as a carrier.
Fig. 3 is a TG curve of the DCOIT sustained release nanocapsules, DCOIT and blank nanocapsules prepared in example 1 using silica as a carrier.
Fig. 4 is a graph showing the sustained release profiles of DCOIT in silica-supported nanocapsules and DCOIT prodrug prepared in example 1 at different temperatures.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the examples are all conventional raw materials and can be obtained commercially, unless otherwise specified; the methods used in the examples are prior art unless otherwise specified.
Example 1
A method for preparing DCOIT sustained-release nano-capsules by taking silicon dioxide as a carrier comprises the following steps:
(1) 0.5mL of APS was added dropwise to 50mL of deionized water with mechanical stirring at 1000rpm for 1min to give an aqueous solution of APS. The positively charged protonated APS now exhibits amphiphilic properties due to protonation of the amino group in this step.
(2) 0.25g of DCOIT and 1mL of MTMS were dissolved in 1mL of xylene, slowly added dropwise to the APS aqueous solution under stirring at 1000rpm for 2min to form an oil-in-water emulsion, and the temperature of the reaction system was adjusted to 25 ℃ and the reaction was stirred for 12 hours.
(3) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal blowing dry oven at 40 ℃ for 12 hours to obtain silica-supported DCOIT sustained-release nanocapsules.
The SEM image of the DCOIT sustained release nanocapsule using silica as a carrier prepared in this example is shown in fig. 1. It can be seen from fig. 1A that the dried nanocapsules maintain a relatively smooth and complete structure with few cracks, indicating that the inner DCOIT component is well protected by the nanocapsule wall structure during the drying process, thereby maintaining the spherical structure of the nanocapsules, which have a particle size of about 600-700nm. Fig. 1B is a scanned image of a few broken nanocapsules, from which it can be seen that the nanocapsules have a distinct hollow structure, forming a microcapsule structure.
The DCOIT sustained-release nanocapsule (drug-loaded nanocapsule), DCOIT and blank nanocapsule (blank nanocapsule is prepared as described in this example, except that DCOIT is not added in step (2)) prepared in this example have an infrared spectrum as shown in fig. 2, and it can be seen from fig. 2 that characteristic peaks of the wall material and the core material appear in the spectrum of the DCOIT nanocapsule, which proves that the prepared nanocapsule successfully coats DCOIT.
The TG curves of the DCOIT sustained-release nanocapsule (drug-loaded nanocapsule), the DCOIT and the blank nanocapsule (preparation method is the same as above) using the silica as the carrier prepared in this embodiment are shown in fig. 3, and as can be seen from fig. 3, the microcapsule has a small mass loss within 230 ℃, which indicates that the microcapsule can maintain the stability of DCOIT to a certain extent, but the wall material structure of the microcapsule is damaged under the condition of high temperature (over 230 ℃), so that the DCOIT is decomposed. In summary, the processing temperature of the microcapsules should not be higher than 230 ℃.
The release curves of the DCOIT sustained-release nanocapsules and the DCOIT technical material prepared by the embodiment using the silicon dioxide as the carrier are shown in fig. 4. As can be seen in fig. 4, the DCOIT prodrug has a faster release rate, and the release is substantially complete at this time as judged by the release trend after 16 h. The release rate of the nano capsule prepared by the embodiment is far less than that of DCOIT raw pesticide, the burst release phenomenon of the pesticide in the initial period of use is effectively slowed down, and the nano capsule has a good slow release effect. The DCOIT in the nanocapsule has the accumulative release of 42.79%, 48.56% and 56.85% at 20, 30 and 40 ℃ respectively; this is due to the fact that as the temperature increases, the brownian motion of the DCOIT molecule increases and the amount released increases; in addition, the expansion of the shell material results in increased porosity and increased number of cracks in the shell layer, which further results in an increased rate of DCOIT release. In conclusion, the nano shell provides a barrier for DCOIT, prolongs the release time of DCOIT and has a good slow-release effect.
The embedding rate (the ratio of the mass of DCOIT in the nanocapsule to the addition amount of DCOIT) and the drug loading rate (the ratio of the mass of DCOIT in the nanocapsule to the mass of the nanocapsule) of the DCOIT sustained-release nanocapsule with silicon dioxide as the carrier obtained in the embodiment are 47.37% and 27.50%; the mass loss is less within 200 ℃ and the thermal stability is good.
Example 2
A method for preparing DCOIT sustained-release nano-capsules by taking silicon dioxide as a carrier comprises the following steps:
(1) 0.25mL of APS was added dropwise to 25mL of deionized water with mechanical stirring at 750rpm for 1min to give an aqueous solution of APS. The positively charged protonated APS now exhibits amphiphilic properties as the amino groups are protonated.
(2) 0.25g of DCOIT and 0.25mL of MTMS were dissolved in 1.0mL of xylene, slowly added dropwise to the APS aqueous solution with stirring at 750rpm for 2min to form an oil-in-water emulsion, the temperature of the reaction system was adjusted to 15 ℃, and the reaction system was allowed to react with stirring for 6 hours and then returned to room temperature.
(3) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal forced air drying oven at 40 ℃ for 12 hours to obtain silica-supported DCOIT extended release nanocapsules.
The DCOIT sustained-release nano-capsule taking silicon dioxide as a carrier obtained in the embodiment has the embedding rate of 44.42 percent and the drug-loading rate of 26.30 percent; the mass loss is less within 200 ℃ and the thermal stability is good.
Example 3
A method for preparing DCOIT sustained-release nano-capsules by taking silicon dioxide as a carrier comprises the following steps:
(1) 0.75mL of APS was added dropwise to 75mL of deionized water with mechanical stirring at 1250rpm for 1min to give an aqueous solution of APS. The positively charged protonated APS now exhibits amphiphilic properties due to protonation of the amino group in this step.
(2) 0.25g of DCOIT and 1.5mL of MTMS were dissolved in 1.0mL of xylene, slowly added dropwise to the APS aqueous solution with stirring at 1250rpm for 2min to form an oil-in-water emulsion, the temperature of the reaction system was adjusted to 35 ℃, and the reaction system was allowed to react with stirring for 18 hours and then returned to room temperature.
(3) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal forced air drying oven at 40 ℃ for 12 hours to obtain silica-supported DCOIT extended release nanocapsules.
The embedding rate of the DCOIT sustained-release nano capsule taking silicon dioxide as a carrier obtained in the embodiment is 47.47%, and the drug loading rate is 26.53%; the mass loss is less within 200 ℃ and the thermal stability is good.
Example 4
A method for preparing DCOIT sustained-release nano-capsules by taking silicon dioxide as a carrier comprises the following steps:
(1) 1.00mL of APS was added dropwise to 50mL of deionized water with mechanical stirring at 750rpm for 1min to give an aqueous solution of APS. The positively charged protonated APS now exhibits amphiphilic properties due to protonation of the amino group in this step.
(2) 0.25g of DCOIT and 1.5mL of MTMS were dissolved in 1.0mL of xylene, slowly added dropwise to the aqueous APS solution with stirring at 750rpm for 2min to form an oil-in-water emulsion, the temperature of the reaction system was adjusted to 45 ℃, and the reaction system was allowed to return to room temperature after stirring for 12 hours.
(3) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal forced air drying oven at 40 ℃ for 12 hours to obtain silica-supported DCOIT extended release nanocapsules.
The embedding rate of the silicon dioxide DCOIT nano-capsule obtained in the embodiment is 43.70%, and the drug loading rate is 25.66%; the mass loss is less within 200 ℃ and the thermal stability is good.
Example 5
A method for preparing DCOIT sustained-release nano-capsules by taking silicon dioxide as a carrier comprises the following steps:
(1) 0.5mL of APS was added dropwise to 25mL of deionized water with mechanical stirring at 500rpm for 1min to give an aqueous solution of APS. The positively charged protonated APS now exhibits amphiphilic properties due to protonation of the amino group in this step.
(2) 0.25g of DCOIT and 0.75mL of MTMS were dissolved in 1.0mL of xylene, slowly added dropwise to the APS aqueous solution with stirring at 500rpm for 2min to form an oil-in-water emulsion, the temperature of the reaction system was adjusted to 25 ℃, and the reaction system was stirred for 24 hours and then returned to room temperature.
(3) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal forced air drying oven at 40 ℃ for 12 hours to obtain silica-supported DCOIT extended release nanocapsules.
The embedding rate of the silica DCOIT nanocapsule obtained in the embodiment is 46.99%, and the drug loading rate is 26.66%; the mass loss is less within 200 ℃ and the thermal stability is good.
Example 6
A method for preparing DCOIT sustained-release nano-capsules by taking silicon dioxide as a carrier comprises the following steps:
(1) 0.25mL of APS was added dropwise to 25mL of deionized water with mechanical stirring at 1000rpm for 1min to give an aqueous solution of APS. The positively charged protonated APS now exhibits amphiphilic properties due to protonation of the amino group in this step.
(2) 0.25g of DCOIT and 0.75mL of MTMS were dissolved in 1.0mL of xylene, slowly added dropwise to the aqueous solution of APS with stirring at 1000rpm for 2min to form an oil-in-water emulsion, the temperature of the reaction system was adjusted to 35 ℃, and the reaction system was allowed to return to room temperature after 6 hours of stirring.
(3) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal forced air drying oven at 40 ℃ for 12 hours to obtain silica-supported DCOIT extended release nanocapsules.
The embedding rate of the silicon dioxide DCOIT nano-capsule obtained in the embodiment is 48.17%, and the drug loading rate is 27.18%; the mass loss is less within 200 ℃ and the thermal stability is good.
Example 7
A method for preparing DCOIT slow-release nano-capsules by using silicon dioxide as a carrier comprises the following steps:
(1) 0.5mL of 3-aminopropylmethyldimethoxysilane was added dropwise to 50mL of deionized water with mechanical stirring at 1000rpm for 1min to give an aqueous solution of 3-aminopropylmethyldimethoxysilane. The positively charged protonated 3-aminopropylmethyldimethoxysilane exhibits amphiphilic properties as the amino groups are protonated in this step.
(2) 0.25g of DCOIT and 1mL of dimethyldimethoxysilane were dissolved in 1mL of xylene, slowly added dropwise to an aqueous solution of 3-aminopropylmethyldimethoxysilane with stirring at 1000rpm for 2min to form an oil-in-water emulsion, and the temperature of the reaction system was adjusted to 25 ℃ and the reaction was stirred for 12 hours.
(3) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal forced air drying oven at 40 ℃ for 12 hours to obtain organically modified silica coated DCOIT extended release nanocapsules.
The comparative example shows that the obtained silica DCOIT nanocapsule has partial breakage (breakage amount is larger than that of example 1) and poor coating effect compared with example 1, the embedding rate is 34.23%, and the drug loading is 16.89%.
Example 8
A method for preparing DCOIT sustained-release nano-capsules by taking silicon dioxide as a carrier comprises the following steps:
(1) 0.5mL of APS was added dropwise to 50mL of deionized water with mechanical stirring at 1000rpm for 1min to give an aqueous solution of APS. The positively charged protonated APS now exhibits amphiphilic properties due to protonation of the amino group in this step.
(2) 0.25g of DCOIT and 2mL of MTMS were dissolved in 1mL of xylene, slowly added dropwise to the aqueous solution of APS with stirring at 1000rpm for 2min to form an oil-in-water emulsion, and the temperature of the reaction system was adjusted to 25 ℃ and the reaction was stirred for 12 hours.
(3) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal blowing dry oven at 40 ℃ for 12 hours to obtain silica-supported DCOIT sustained-release nanocapsules.
The DCOIT sustained-release nano-capsule taking silicon dioxide as a carrier obtained in the embodiment has the embedding rate of 35.42 percent and the drug-loading rate of 20.22 percent; the mass loss is less within 200 ℃ and the thermal stability is good.
Comparative example 1
A method for preparing DCOIT sustained-release nano-capsules by taking silicon dioxide as a carrier comprises the following steps:
(1) 0.25g of DCOIT, 0.5mL of APS and 1.0mL of MTMS were dissolved in 1.0mL of xylene, slowly added dropwise to 50mL of deionized water under mechanical stirring at 1000rpm for 2min to form an oil-in-water emulsion, and the temperature of the reaction system was adjusted to 25 ℃ and stirred for 12 hours.
(2) The nanocapsules were then separated from the mixture using a centrifuge, followed by washing with distilled water 3 times and drying in an electrothermal forced air drying oven at 40 ℃ for 12 hours to obtain organically modified silica coated DCOIT extended release nanocapsules.
Compared with example 1, the particle size distribution of the obtained silica DCOIT nano-capsule is uneven, and the coating effect is not good, namely, the embedding rate is 37.12 percent, and the drug loading rate is 19.44 percent.
The above detailed description of the preferred embodiments of the present invention and the corresponding comparative examples is the result of many experiments conducted by the inventors in a considerable amount of time. It will be apparent to those skilled in the art that various modifications and adaptations to these embodiments may be made without the use of inventive faculty. Therefore, any technical solutions that can be obtained by those skilled in the art without departing from the present invention should be within the protection scope of the present invention.
Claims (10)
1. The DCOIT slow-release nanocapsule taking silicon dioxide as a carrier is characterized in that the nanocapsule comprises a core material and a wall material; the core material is a xylene solution of DCOIT; the wall material is organic modified silicon dioxide and is formed by the autocatalytic reaction of amino alkoxy silane and alkoxy silane at an oil-water interface.
2. The silica-supported DCOIT extended release nanocapsule of claim 1, wherein the nanocapsule has a micro-morphology comprising: nanospheres with particle size of 500-800 nm.
3. A process for the preparation of silica-supported DCOIT extended release nanocapsules as claimed in claim 1 or 2, comprising the steps of:
(1) Under the condition of stirring, dropwise adding amino alkoxy silane into deionized water to obtain an amino alkoxy silane aqueous solution;
(2) Dissolving DCOIT and alkoxy silane in xylene to obtain a mixed solution; and slowly dripping the mixed solution into the amino alkoxy silane aqueous solution under the stirring condition, reacting under stirring, and separating, washing and drying the obtained reaction solution to obtain the DCOIT slow-release nano capsule taking silicon dioxide as a carrier.
4. The method for preparing DCOIT sustained-release nanocapsules using silica as a carrier according to claim 3, wherein in the step (1), the aminoalkoxysilane is one or a combination of more than two of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane; preferably, the aminoalkoxysilane is 3-Aminopropyltrimethoxysilane (APS).
5. The method of preparing the DCOIT extended release nanocapsule of claim 3 wherein the silica is supported on one or more of the following conditions:
i. in the steps (1) and (2), the stirring speed is 500-1250rpm;
ii. In the step (1), the volume ratio of the amino alkoxy silane to the deionized water is 1.
6. The method for preparing DCOIT slow-release nanocapsule using silica as carrier according to claim 3, wherein in the step (2), the alkoxysilane is one or a combination of two or more of tetraethyl orthosilicate, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, or diethyldiethoxysilane; preferably, the alkoxysilane is methyltrimethoxysilane (MTMS).
7. The method for preparing the DCOIT extended release nanocapsule as claimed in claim 3, wherein step (2) comprises one or more of the following conditions:
i. the volume ratio of alkoxysilane to xylene is from 0.2 to 1, preferably from 0.25 to 1.5;
ii. The mass of DCOIT and the volume ratio of xylene are 0.1-0.5.
8. The method for preparing DCOIT sustained-release nanocapsule using silica as a carrier according to claim 3, wherein in the step (2), the volume ratio of the alkoxysilane in the mixed solution to the aminoalkoxysilane in the aminoalkoxysilane aqueous solution in the step (1) is 1 to 3.
9. The method for preparing the DCOIT extended release nanocapsule as claimed in claim 3, wherein step (2) comprises one or more of the following conditions:
i. the reaction temperature is 15-45 ℃; the reaction time is 6-24h;
ii. The separation is to separate the nano capsules by using a centrifugal machine; the washing is 3-5 times by using water; the drying is carried out for 12-24h at the temperature of 30-50 ℃;
and iii, the dropping speed is 0.5-2mL/min.
10. Use of the silica-supported DCOIT extended release nanocapsule of claim 1 or 2 as a functional chemical additive for preventing fungal and bacterial growth; preferably, the nanocapsules are applied as an additive in paints, rubbers, plastics, lubricants or wood.
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