CN109180985A - It is a kind of to utilize the hollow mesoporous SiO of micron order2The anticoagulant water medical silica-gel material that microballoon and PDMS blended cross linking are modified - Google Patents

It is a kind of to utilize the hollow mesoporous SiO of micron order2The anticoagulant water medical silica-gel material that microballoon and PDMS blended cross linking are modified Download PDF

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CN109180985A
CN109180985A CN201811337116.9A CN201811337116A CN109180985A CN 109180985 A CN109180985 A CN 109180985A CN 201811337116 A CN201811337116 A CN 201811337116A CN 109180985 A CN109180985 A CN 109180985A
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microballoon
hollow mesoporous
sio
mesoporous sio
anticoagulant
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CN109180985B (en
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陈剑
黄斌
陶小根
孔源
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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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The hollow mesoporous SiO of micron order is utilized the invention discloses a kind of2The anticoagulant water medical silica-gel material that microballoon and PDMS blended cross linking are modified, using the hollow mesoporous SiO of novel micron order response type2Microballoon, as crosslinking agent, with current breathing machine pipeline silicon rubber substrate, dimethyl silicone polymer (PDMS) is blended, and obtains the silicon rubber substrate of the stable porous microsphere doping of performance.Mesoporous hollow SiO2Microballoon can not only play function of heat insulation, can also load small molecule bacteriostatic agent wherein, and mesoporous lamella makes bacteriostatic agent slow release in the substrate, plays the role of pipeline bacterioistatic.Finally in one layer of nanoscale SiO of Silica Surface fixation in situ2The super hydrophilic layer of particle inhibits water droplet in Surface Creation, to prepare collection heat preservation insulation, anticoagulant water and the integrated new medical silastic material of bacteria resistance function.

Description

It is a kind of to utilize the hollow mesoporous SiO of micron order2Microballoon and PDMS blended cross linking are modified anti- Condensate medical silica-gel material
Technical field
The invention belongs to medical material tech fields, and in particular to a kind of to utilize the hollow mesoporous SiO of micron order2Microballoon with The modified anticoagulant water medical silica-gel material of PDMS blended cross linking.
Background technique
Severe medicine is grown rapidly, and mechanical ventilation is played an important role during giving treatment to patient with severe symptoms.But it is exhaled in use During suction machine mechanical ventilation, due to carrying out warming humidification and exhaled gas to sucking gas, there are the temperature difference with environment, exhale It sucks back Lu Zhongchang and generates a large amount of condensed water (800-1000ml/ days).Condensed water is directly entered in pipeline or respiratory tract, is caused Pipeline ponding is unsmooth, ventilator false triggering, and man-machine confrontation increases, and in turn results in the increase of patient respiratory load, can lead to when serious Airway damage, pneumothorax, deficient airway etc. and jeopardize patient vitals.
The generation placed in gas supply pipeline and heat seal wire to reduce condensed water is mostly used at present, and is set in breathing circuit Enter collecting bowl and promotes the methods of condensed water drainage to reduce medical-risk caused by condensation dilutional hyponatremia.But the above method exists not Foot, be such as difficult to realize accurately temperature regulation, be not placed in heating seal wire in gas exhaust piping, patient with severe symptoms carries out replacement position and shield Situations such as collecting bowl is obviously tilted or is inverted easily occurs often for reason operation.Condensed water in breathing machine pipeline and collecting bowl is also thin The important place of bacterium breeding, according to statistics, positive rate of bacteria is up to 86.7%, and find to be turned out by sputum Lai it is thin Culture bacterium has high consistency in bacterium and condensed water.It may be up to 2*10 close to bacterial concentration in the condensed water at conduit5cfu/ Ml increases the incidence of Ventilator Associated Pneumonia, brings great difficulty to medical treatment sense prevention and control.Above situation can lead to ICU A series of problems, such as length of patient stay extends, and medical expense increases, and medical and nursing work amount increases, brings to patient home and society Heavy burden, so being that ICU clinic is difficult to evade, but there is an urgent need to solve in breathing machine pipeline circuit the problem of condensate water-proof One of problem certainly.
At present either by reequiping collecting bowl or being placed in this two kinds of mainstreams reduction pipeline condensed waters of pipeline heating seal wire Mode produces little effect in clinical practice, to find out its cause, failing fundamentally to solve current silica gel piping material insulation effect Difference causes the moisture in pipeline in warm air to condense rapidly so that can carry out heat exchange inside and outside pipeline rapidly, generates a large amount of The problem of condensed water.For the above reasons, it is desirable to by studying existing ventilator circuit silicone rubber material, change substrate Own physical structure or the thermal and insulating performance that substrate modifications are improved with tubing itself, or coat on the surface of the material super hydrophilic anti- Mist coating inhibits water vapour to condense on surface, to be formed from preventing breathing pipeline condensed water at all.On the other hand, pipeline is set Enter fungistatic coating, certain disinfection can be played to condensed water in pipeline and excreta, reduces rate of hospital acquired infection.Therefore, It such as fights the preparation of condensate silica gel material and performance improvement is successfully applied in the preparation of medical respiration pipeline silica gel material, it will very The condensate flow that medical respiration pipeline is reduced in big degree, reduces a possibility that iatrogenic accident occurs for patient, prevents the generation of VAP With reduction bacterial resistance, medical and nursing work efficiency is greatly improved, saves social resources.
Now from ICU clinical practice problem, propose that carrying out actual functional capability to widely available breathing machine pipeline material changes Into not only the clinical big practical challenges of solution, the more exploitation of medicinal intelligent safe silica gel material provide new approaches and new method.
Summary of the invention
Hollow Jie of micron order is utilized the technical problem to be solved by the present invention for the above-mentioned state of the art is to provide a kind of Hole SiO2The anticoagulant water medical silica-gel material that microballoon and PDMS blended cross linking are modified.
The technical scheme of the invention to solve the technical problem is:
It is a kind of to utilize the hollow mesoporous SiO of micron order2The anticoagulant water medical silica-gel material that microballoon and PDMS blended cross linking are modified, It is characterized in that, preparation method the following steps are included:
(1) the hollow mesoporous SiO of micron order2Microballoon synthesis:
I) polystyrene microsphere is prepared using soap-free emulsion method, initiator uses water-soluble potassium peroxydisulfate, in nitrogen Under protection, the two reaction is allowed to obtain mono dispersed micrograde polystyrene moulding microballoon for 24 hours under 70 DEG C of temperature environments；
Ii) the polystyrene moulding microballoon of step i) is dispersed in the ethanol water containing micro tetraethyl orthosilicate, Appropriate ammonium hydroxide is added dropwise, room temperature reaction carries out hydroxyl modification for 24 hours, in polystyrene moulding microsphere surface；
Iii) into step ii), cetyl trimethylammonium bromide, hexamethylene and tetraethyl orthosilicate is added in reaction system, 50 DEG C of -55 DEG C of reactions a period of times, hollow mesoporous SiO can be obtained2Microballoon；
Iiii) by hollow mesoporous SiO2Microballoon is dispersed in benzalkonium bromide solution, hollow mesoporous SiO2Small point on micro-ball load Sub- bacteriostatic agent；
(2) the hollow mesoporous SiO of micron order2The synthesis of micro-sphere crosslinked silica gel:
Hollow mesoporous SiO of the surface containing great amount of hydroxy group prepared by step (1)2Microballoon and dimethyl silicone polymer are blended, Octoate catalyst stannous is added, silicon rubber is made；
(3) silastic surface Nano-meter SiO_22The modification of particle super-hydrophilic coating:
The solid SiO of 50nm or so is prepared using sol-gel method2Nanoparticle is dispersed in TEOS ethanol solution, adopts One layer of nanoparticle is uniformly coated in silastic surface with spin-coating method or immersion czochralski method, a small amount of ammonium hydroxide is being added dropwise, is making nanoparticle It is crosslinked between son, particle layer is fixed on silastic surface.
Beneficial effects of the present invention:
1. the present invention studies existing ventilator circuit silicone rubber material, change substrate own physical structure or to base The modified thermal and insulating performance for improving tubing itself of material, and then breathing circuit condensed water is asked when fundamentally solving mechanical ventilation Topic.
2. plastics on new materials breathing circuit saves production cost, simplifies pipeline installation, reduce work without installing the cup device that catchments Make load.
3. applying hollow mesoporous SiO2Microballoon replaces common small molecule silica gel agent, cleverly that porous heat insulation material is steady Fixed is introduced into silica gel substrate, realizes material heat insulating function, prevents breathing circuit gas temperature from losing, hence it is evident that reduces pipeline condensation Water is formed.
4. making heat-insulated silica gel material form superhydrophilic surface by modifying material surface, surface preventing atomization is improved Can, further such that steam can not be condensed in silica gel tube wall surface, pipeline is difficult to form water flow, avoids the mistake touching of ventilator Hair, utmostly reduces man-machine confrontation, provides accurately respiratory mechanics monitor index, provides breathing branch for severe respiratory failure It holds.
6. material load is made to ease up hold-off microbial inoculum, heat-insulated and antibacterial economic benefits and social benefits function is realized, it can be to breathing out secretion in pipeline And pipeline condensed water preliminarily pasteurized, pollution is reduced, is played an important role to institute's sense prevention and control.
7. plastics on new materials pipeline is different from existing disposable breathing pipeline material, not easily damaged and differentiation, properties constant can Tolerance disinfection and supply center wash repeatedly, sterilize and drying and processing, meets circulating repetition use, reduces medical treatment cost, saving is greatly Measure social resources.
Detailed description of the invention
The following further describes the present invention with reference to the drawings.
Fig. 1 is silica gel material preparation technology flow chart of the present invention.
Fig. 2 is the hollow mesoporous SiO of the present invention2Microballoon composition principle schematic diagram.
Fig. 3 is bacteriostatic agent of the present invention in hollow mesoporous SiO2Load principle figure in microballoon.
Fig. 4 is the hollow mesoporous SiO of the present invention2Microballoon and PMDS blended cross linking schematic illustration.
Fig. 5 is silastic surface Nano-meter SiO_2 of the present invention2Particle super-hydrophilic coating modifies schematic illustration.
Specific embodiment
Present invention is further described in detail with reference to the accompanying drawings and detailed description.
As shown in Figs. 1-5, a kind of to utilize the hollow mesoporous SiO of micron order2The anticoagulant water that microballoon and PDMS blended cross linking are modified Medical silica-gel material, preparation method the following steps are included:
(1) the hollow mesoporous SiO of micron order2Microballoon synthesis:
I) polystyrene microsphere is prepared using soap-free emulsion method, initiator uses water-soluble potassium peroxydisulfate, in nitrogen Under protection, the two reaction is allowed to obtain mono dispersed micrograde polystyrene moulding microballoon for 24 hours under 70 DEG C of temperature environments；
Ii) the polystyrene moulding microballoon of step i) is dispersed in the ethanol water containing micro tetraethyl orthosilicate, Appropriate ammonium hydroxide is added dropwise, room temperature reaction carries out hydroxyl modification for 24 hours, in polystyrene moulding microsphere surface；
Iii) into step ii), cetyl trimethylammonium bromide, hexamethylene and tetraethyl orthosilicate is added in reaction system, 50 DEG C of -55 DEG C of reactions a period of times, hollow mesoporous SiO can be obtained2Microballoon；
Iiii) by hollow mesoporous SiO2Microballoon is dispersed in benzalkonium bromide solution, hollow mesoporous SiO2Small point on micro-ball load Sub- bacteriostatic agent；
(2) the hollow mesoporous SiO of micron order2The synthesis of micro-sphere crosslinked silica gel:
Hollow mesoporous SiO of the surface containing great amount of hydroxy group prepared by step (1)2Microballoon and dimethyl silicone polymer are blended, Octoate catalyst stannous is added, silicon rubber is made；
(3) silastic surface Nano-meter SiO_22The modification of particle super-hydrophilic coating:
The solid SiO of 50nm or so is prepared using sol-gel method2Nanoparticle is dispersed in TEOS ethanol solution, adopts One layer of nanoparticle is uniformly coated in silastic surface with spin-coating method or immersion czochralski method, a small amount of ammonium hydroxide is being added dropwise, is making nanoparticle It is crosslinked between son, particle layer is fixed on silastic surface.
The research of the aqueous energy of silastic material condensation-resistant of the present invention:
After silicon rubber is crosslinked in tubular die, takes out, is carried out on simulated respiration pipeline:
A. prepared two sections, total 25cm of cross-linked silicone rubber pipe (experimental group) is taken, as suction line, is connected with Y type connecting tube It connects, collecting bowl A1 is installed below Y-piece, thermometer 1 and thermometer 2 are installed in pipeline section start and end respectively, and same method exists Collecting bowl B1 is installed in expiration pipeline, is sequentially connected ventilator, 810 humidification pots and manual simulation's lung.
B. two sections, total 25cm of conventional ventilator tube silica gel screwed pipe (control group) are taken, as suction line, is connected with Y type Collecting bowl A2 is installed in adapter tube connection, Y-piece lower section, and thermometer 3 and thermometer 4 are installed in pipeline section start and end respectively, equally Method installs collecting bowl B2 in expiration pipeline, is sequentially connected ventilator, 810 humidification pots and manual simulation's lung.
C. mechanical ventilation 24 hours collect A1, B1, A2, B2 condensation water quantity in every 2 hours respectively, record data, compare A1+ B1 and A2+B2 condensation water quantity, statistical analysis such as the following table 1.
Table 1
D. according to table analysis results, material line condensation-resistant of the present invention is aqueous to be substantially better than traditional silica gel material.
The research of silastic material thermal insulation property of the present invention:
A. prepared two sections, total 25cm of cross-linked silicone rubber pipe (experimental group) is taken, as suction line, is connected with Y type connecting tube It connects, collecting bowl A1 is installed below Y-piece, thermometer 1 and thermometer 2 are installed in pipeline section start and end respectively, and same method exists Collecting bowl B1, connection ventilator, 810 humidification pots and manual simulation's lung are installed in expiration pipeline.
B. two sections, total 25cm of conventional ventilator tube silica gel screwed pipe (control group) are taken, as suction line, is connected with Y type Collecting bowl A2 is installed in adapter tube connection, Y-piece lower section, and thermometer 3 and thermometer 4 are installed in pipeline section start and end respectively, equally Method installs collecting bowl B2, connection ventilator, 810 humidification pots and manual simulation's lung in expiration pipeline.
C. mechanical ventilation 24 hours, every 2 hours difference recording thermometers 1, thermometer 2, thermometer 3, the cold temperature of thermometer 4 And room temperature T0, comparison temperature meter 1 and thermometer 2, thermometer 1 and thermometer 3, thermometer 3 and 4 temperature difference of thermometer, statistics Table such as the following table 2.
Table 2
D. it is analyzed according to table 2 as a result, material line thermal insulation property of the present invention is substantially better than existing traditional silastic material.
The research of silastic material bacteriostasis property of the present invention:
A. prepared two sections, total 25cm of cross-linked silicone rubber pipe (experimental group) is taken, as suction line, is connected with Y type connecting tube It connects, collecting bowl A1 is installed below Y-piece, thermometer 1 and thermometer 2, the choosing of expiration pipeline are installed in pipeline section start and end respectively It takes containing prepared cross-linked silicone rubber pipe, is inoculated with streptococcus pneumonia, staphylococcus epidermis respectively in simulated lung expiration proximal end, with same Method installs collecting bowl B1, connection ventilator, 810 humidification pots and manual simulation's lung in expiration pipeline.
B. two sections, total 25cm of conventional ventilator tube silica gel screwed pipe (control group) are taken, as suction line, is connected with Y type Collecting bowl A2 is installed in adapter tube connection, Y-piece lower section, and thermometer 3 and thermometer 4 are installed in pipeline section start and end respectively, equally Method installs collecting bowl B2, connection ventilator, 810 humidification pots and manual simulation's lung in expiration pipeline (no antimicrobial coating).
C. mechanical ventilation 168 hours, respectively in 48h, 72h, 168h sterile eluent leaching being soaked with containing corresponding neutralizer Wet cotton swab directly smears breathing circuit end and the B1 and B2 that catchments.Sampling pipe is vibrated into 20s on vortex mixer, with nothing Bacterium suction pipe draws 1.0ml measuring samples and is inoculated in sterilizing plates, is placed in (36 ± 1) DEG C incubator culture 48h.Compare different parts The case where bacterial growth, bacterium colony counts and the correlation with the time.Hand hygiene specification, rigorous aseptic behaviour are executed in sampling process Make.Statistical result such as the following table 3.
Table 3
Based on the analysis results, compare two kinds of material line bacteriostasis properties, hence it is evident that silastic material of the invention is by antibacterial The gap addition fungistatic effect of agent is substantially better than existing breathing pipeline.
Above content is only citing made for the present invention and explanation, affiliated those skilled in the art are to being retouched The specific embodiment stated does various modifications or additions or is substituted in a similar manner, as long as it does not deviate from the concept of invention Or beyond the scope defined by this claim, it is within the scope of protection of the invention.

Claims (1)

1. a kind of utilize the hollow mesoporous SiO of micron order2The anticoagulant water medical silica-gel material that microballoon and PDMS blended cross linking are modified, Be characterized in that, preparation method the following steps are included:
(1) the hollow mesoporous SiO of micron order2Microballoon synthesis:
I) polystyrene microsphere is prepared using soap-free emulsion method, initiator uses water-soluble potassium peroxydisulfate, in nitrogen protection Under, allow the two reaction to obtain mono dispersed micrograde polystyrene moulding microballoon for 24 hours under 70 DEG C of temperature environments；
Ii) the polystyrene moulding microballoon of step i) is dispersed in the ethanol water containing micro tetraethyl orthosilicate, is added dropwise Appropriate ammonium hydroxide, room temperature reaction carry out hydroxyl modification for 24 hours, in polystyrene moulding microsphere surface；
Iii) reaction system addition cetyl trimethylammonium bromide, hexamethylene and tetraethyl orthosilicate into step ii), 50 DEG C of -55 DEG C reactions a period of times, hollow mesoporous SiO can be obtained2Microballoon；
Iiii) by hollow mesoporous SiO2Microballoon is dispersed in benzalkonium bromide solution, hollow mesoporous SiO2Small molecule presses down on micro-ball load Microbial inoculum；
(2) the hollow mesoporous SiO of micron order2The synthesis of micro-sphere crosslinked silica gel:
Hollow mesoporous SiO of the surface containing great amount of hydroxy group prepared by step (1)2Microballoon and dimethyl silicone polymer are blended, and addition is urged Silicon rubber is made in agent stannous octoate；
(3) silastic surface Nano-meter SiO_22The modification of particle super-hydrophilic coating:
The solid SiO of 50nm or so is prepared using sol-gel method2Nanoparticle is dispersed in TEOS ethanol solution, using spin coating Method impregnates czochralski method and in silastic surface uniformly coats one layer of nanoparticle, and a small amount of ammonium hydroxide is being added dropwise, is making between nanoparticle Crosslinking, particle layer are fixed on silastic surface.
CN201811337116.9A 2018-11-12 2018-11-12 SiO utilizing micron-sized hollow mesoporous2Microsphere and PDMS (polydimethylsiloxane) blending crosslinking modified anti-freezing medical silica gel material Active CN109180985B (en)

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CN117983298A (en) * 2024-03-29 2024-05-07 岳阳兴长石化股份有限公司 Crosslinked polystyrene hollow microsphere catalyst and preparation method and application thereof

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