CN105949720B - Nanocomposite foaming agent, foaming product and its preparation method and application - Google Patents

Nanocomposite foaming agent, foaming product and its preparation method and application Download PDF

Info

Publication number
CN105949720B
CN105949720B CN201610333686.5A CN201610333686A CN105949720B CN 105949720 B CN105949720 B CN 105949720B CN 201610333686 A CN201610333686 A CN 201610333686A CN 105949720 B CN105949720 B CN 105949720B
Authority
CN
China
Prior art keywords
preparation
foaming agent
silicon oxide
mesoporous silicon
nanocomposite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610333686.5A
Other languages
Chinese (zh)
Other versions
CN105949720A (en
Inventor
郭灿雄
王足远
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN201610333686.5A priority Critical patent/CN105949720B/en
Publication of CN105949720A publication Critical patent/CN105949720A/en
Application granted granted Critical
Publication of CN105949720B publication Critical patent/CN105949720B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silicon Compounds (AREA)

Abstract

The present invention relates to foaming agent fields, and in particular to nanocomposite foaming agent, foaming product and its preparation method and application.The nanocomposite foaming agent is it is characterized in that, by modified mesoporous silicon oxide and 4, and the double benzsulfamides of 4 '-oxos are combined, the modified mesoporous silicon oxide and 4, and the mass ratio of the double benzsulfamides of 4 '-oxos is 1:(3-7)；Wherein, the modified mesoporous silicon oxide is successively obtained after reaming and graft modification by mesoporous silicon oxide.Not only particle size is small for nanocomposite foaming agent of the present invention, but also to the loading of chemical foaming agent height, so as to obtain the better microcellular foam of foaming quality, has broad application prospects.

Description

Nanocomposite foaming agent, foaming product and its preparation method and application
Technical field
The present invention relates to foaming agent fields, relate generally to composite foamable agent field, and in particular to nanocomposite foaming agent, hair Brewage and its preparation method and application.
Background technique
Mesoporous nano composite material is that nano particle or cluster are filled into formed in the gap with meso-scale Complex, since confinement effect and interface coupling act on, the Mesoporous Composites of this heterogeneous out-phase, which have, is both different from nanometer Particle is different from the property of common mesoporous material itself again.Metaporous silicon dioxide material has biggish specific surface area and hole Volume, and aperture and pattern have adjustable denaturation, are increasingly becoming most common carrier material in mesoporous nano composite material.
Microcellular foam refers to and cell diameter foamed plastics less than 100 μm uniform in distribution of cells, typical micro- Hole plastics abscess cell diameter is 5~50 μm, and cell density is up to 109~1012A/cm3.Microcellular foam is that a kind of lightweight is new Profile material, its design concept are small using evenly dispersed fine and close and minimum abscess, these small cells in a polymer matrix In the intrinsic small crack of plastics itself or small defect, plays the role of stress concentration, produce multiple crazing, be passivated and split Line tip, slows down crack growth so that microcellular foam have thermal stability more more excellent than conventional foams and Mechanical property, lower dielectric constant and better insulating properties.
Currently, preparing foaming agent used by foamed plastics, there are two main classes, and one kind is physical blowing agent, and one kind is chemistry Foaming agent.It microcellular foam is prepared using physical blowing agent generally includes monomer polymerization method, supercritical fluid precipitation method, heat and draw Phase separation method and supersaturated gas method are led, the most commonly used is supercritical fluid precipitation methods, but with CO2For the overcritical of representative The fluid physics foaming agent feature that dissolubility is low, diffusivity is high in the polymer keeps the abscess pattern for controlling foamed plastic very tired Difficulty, and equipment joint cost is high, the experiment conditions such as required sharply decompression or heating are not easily accomplished, mass production cellular plastic Product or difficult point.When preparing foamed plastics using chemical foaming agent method, chemical foaming agent can not be due to electrostatic agglomeration effect It is evenly dispersed in polymer, and foaming process lacks nucleating point, foaming quality is poor, it is difficult to obtain microcellular foam.
Patent (application No. is 201010176081.2) provides a kind of nano combined foaming based on porous inorganic material Agent: after porous inorganic material is modified, the object of composite foamable agent being dissolved in certain quantitative solvent, and modified Porous inorganic material is compound, is separated after a period of time, dries obtained nanocomposite foaming agent.Although this patent can be in certain journey Solve the problems, such as that foaming agent is reunited on degree, but its load capacity of organic foaming agent object on porous inorganic material is still improved The bubbling efficiency in space, nanocomposite foaming agent is still to be improved.
Patent (application No. is 201410051937.1) provides a kind of nanocomposite foaming agent: stratiform montmorillonite is carried out After removing, by itself and 4, the recombination of 4- oxobenzenesulfonyl hydrazide is compound, but stratiform montmorillonite makes interlayer due to its structure feature The foaming agent of load is easier to be eluted by solvent, and the nanocomposite foaming agent particle size being prepared is larger, is distributed not equal enough Even, property is still to be improved.
Summary of the invention
Technical problem solved by the present invention is although existing composite foamable agent can solve abscess-size hardly possible to a certain extent The problem of to control, but at present foaming agent composite effect it is still to be improved, the nucleating point on composite foamable agent still have it is to be increased, It still needs further improvement for bubbling efficiency and quality.
The purpose of the present invention is: based on silica, a kind of nanocomposite foaming agent is provided, by silica Reaming and modification are carried out, the combination process of silica and organic foaming agent is optimized, so that combined efficiency is improved, into one Step improves bubbling efficiency and quality.
In order to solve the above technical problems, the present invention provides a kind of nanocomposite foaming agents, wherein the nano combined hair Infusion contains chemical foaming agent and the successively mesoporous silicon oxide Jing Guo reaming, modification (MS), and the reaming silica is logical It crosses and impregnates silica and alkali metal salt or double salt, the modification reaming silica is by by reaming silica It is YRnSiX with general formula3Silane coupling agent reaction and be made, wherein Y is organic compound functional group, and R is methylene or benzene Base, X are hydrolyzable functional groups.
The present invention also provides a kind of preparation methods of nanocomposite foaming agent, this method comprises: existing in organic solvent Under conditions of, it successively will sufficiently be washed after the mesoporous silicon oxide of reaming, modification and chemical foaming agent are mixed, it is described Reaming silica by the way that silica and alkali metal salt or double salt are impregnated, the modification reaming silica is logical Crossing reaming silica and general formula is YRnSiX3The silane coupling agent reaction of (wherein n=1 or >=3) is made, and wherein Y is that have Machine compound functional group, R are methylene or phenyl, and X is hydrolyzable functional group, and the cleaning solvent includes the mixed of alcohol and alcohol Close solution.
In the present invention, term " mesoporous " refers to that average pore diameter is the hole between 2-50 nanometers, that is to say, that mesoporous Material refers to material of the average pore diameter between 2 nanometers and 50 nanometers；Term " nano combined " refers in composite material Filling phase at least one dimension has nanoscale, and packet expands nano particle structure in the form of sheets, only one-dimensional in nanoscale, nanometer Particle is in rodlike, and bidimensional is in nanoscale and nano particle is in chondritic, and three-dimensional is in nanoscale.In the third material It further include particle size is micron-sized in material, but pore size is nanoscale spheric granules.
The present invention also provides the applications that above-mentioned nanocomposite foaming agent prepares foaming product and microcellular foam.
Specifically, in view of the deficiencies of the prior art, the present invention provides the following technical scheme that
A kind of nanocomposite foaming agent, which is characterized in that by modified mesoporous silicon oxide and 4, the double benzsulfamides of 4 '-oxos It is combined, the mass ratio of the modified mesoporous silicon oxide and 4, the double benzsulfamides of 4 '-oxos is 1:(3-7)；Wherein, described Modified mesoporous silicon oxide is successively obtained after reaming and graft modification by mesoporous silicon oxide.
Preferably, in above-mentioned nanocomposite foaming agent, the modified mesoporous silicon oxide and 4, the double benzsulfamides of 4 '-oxos Mass ratio be 1:(4-6).
Preferably, in above-mentioned nanocomposite foaming agent, the partial size of the nanocomposite foaming agent is 0.8-10 μm, preferably 0.4-6.5 μm, more preferably 0.4-1 μm.
Preferably, in above-mentioned nanocomposite foaming agent, the aperture of the mesoporous silicon oxide is 2-40nm, preferably 10- 36nm。
Preferably, in above-mentioned nanocomposite foaming agent, the partial size of the mesoporous silicon oxide is 0.1-2 μm, preferably 0.4-1.5μm。
The present invention also provides the preparation methods of above-mentioned nanocomposite foaming agent, it is characterised in that: to mesoporous silicon oxide according to It is secondary after reaming and graft modification, obtain modified mesoporous silicon oxide；It will modified mesoporous silicon oxide and the double benzene of 4,4 '-oxos Sulfonamide is compound to obtain nanocomposite foaming agent, wherein the modified mesoporous silicon oxide and 4, the double benzsulfamides of 4 '-oxos Mass ratio is 1:(3-7).
Preferably, in above-mentioned preparation method, the preparation method of the nanocomposite foaming agent includes the following steps:
(1) expanding treatment is carried out to mesoporous silicon oxide with salt impregnation method；
(2) mesoporous silicon oxide after reaming is added in modifying agent and is modified, obtain modified mesoporous silicon oxide；
(3) N of the double benzsulfamides of 4,4 '-oxos will be contained, above-mentioned modification mesoporous two is added in N '-dimethyl formamide solution In silica, successively after ultrasound, washing, nanocomposite foaming agent is obtained.
Preferably, in above-mentioned preparation method, the preparation method of the nanocomposite foaming agent includes the following steps:
(1) expanding treatment is carried out to mesoporous silicon oxide with salt impregnation method；
(2) it disperses the mesoporous silicon oxide after reaming in ethanol water, after sonicated, is added in modifying agent It is modified, obtains modified mesoporous silicon oxide；
(3) above-mentioned modified meso-porous titanium dioxide is added in the dimethyl formamide solution that will contain the double benzsulfamides of 4,4 '-oxos In silicon, successively after ultrasound, washing, nanocomposite foaming agent is obtained.
Preferably, in above-mentioned preparation method, the salt used in salt impregnation method described in step (1) include it is one or two kinds of with The mixture of upper alkali metal salt；The mass concentration of the alkali metal salt is 5-70%, preferably 20-30%.
Preferably, in above-mentioned preparation method, the alkali metal salt is the one or two of sodium chloride, lithium chloride or potassium nitrate The double salt of composition described above.
Preferably, in above-mentioned preparation method, the mass ratio of the double salt are as follows: sodium chloride: lithium chloride: sodium nitrate=(3-5): 1:1。
Preferably, in above-mentioned preparation method, the process of expanding treatment described in step (1) includes the following steps:
After salting liquid is added in mesoporous silicon oxide, calcined with programmed temperature method, described program temperature-rise period includes Following step:
(1) temperature is risen into the first calcination temperature, constant temperature 30-60min from room temperature；
(2) temperature is warming up to the second calcination temperature, constant temperature 3-5h from the first calcination temperature；
Wherein, first calcination temperature is 200-300 DEG C, and the second calcination temperature is 400-700 DEG C.
Preferably, in above-mentioned preparation method, the ratio of the mesoporous silicon oxide and salting liquid is 1g:(0.1-100) ml.
Preferably, in above-mentioned preparation method, the dip time of the mesoporous silicon oxide and salting liquid is 3-24h.
Preferably, in above-mentioned preparation method, the preparation process of the mesoporous silicon oxide includes the following steps:
Ethyl orthosilicate is added in the organic solvent containing cetylamine, calcining obtains mesoporous silicon oxide；The positive silicon The ratio of acetoacetic ester and cetylamine is (30-40) ml:(5-7) g.
Preferably, in above-mentioned preparation method, the calcination process is Temperature Programmed Processes, is included the following steps:
(1) temperature is risen into the first calcination temperature, constant temperature 30-60min from room temperature.
(2) temperature is warming up to the second calcination temperature, constant temperature 30-60min from the first calcination temperature.
(3) temperature is warming up to third calcination temperature, constant temperature 3-5h from the second calcination temperature.
Wherein, first calcination temperature is 200-300 DEG C, and the second calcination temperature is 400-500 DEG C, third calcination temperature It is 600-800 DEG C.
Preferably, in above-mentioned preparation method, the modifying agent is silane coupling agent, preferably gamma-aminopropyl-triethoxy Silane, γ-glycidyl ether oxygen propyl trimethyl silane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
Preferably, in above-mentioned preparation method, the ratio of the silane coupling agent and mesoporous silicon oxide is (1-6) ml:1g, Preferably (4-6) ml:1g.
Preferably, in above-mentioned preparation method, the modification temperature is 25-60 DEG C, preferably 25 DEG C.
Preferably, in above-mentioned preparation method, the N of the double benzsulfamides of 4,4 '-oxos, N '-diformazan are contained described in step (3) In base formamide solution, the concentration of the double benzsulfamides of 4,4 '-oxos is 0.2mo/L~0.5mol/L, preferably 0.4-0.5mol/ L。
Preferably, in above-mentioned preparation method, ultrasonic time is 10-30min in step (2) and step (3).
Preferably, in above-mentioned preparation method, washing lotion used in washing process described in step (3) includes methanol.
Preferably, in above-mentioned preparation method, the washing process includes the following steps:
(1) it is washed with mixing washing lotion；
(2) it is washed with methanol；
Wherein, the mixing washing lotion includes methanol, 4, the double benzsulfamides of 4 '-oxos and N, N '-dimethyl formamide.
Preferably, in above-mentioned preparation method, in the mixing washing lotion, with the double benzenesulfonamides of every gram of 4,4 '-oxos, including The methanol of 5-15ml and the N of 5-15ml, N '-dimethyl formamide, the preferably N of the methanol of 5-10ml and 5-10ml, N '-diformazan Base formamide.
The present invention also provides a kind of nanocomposite foaming agents, which is characterized in that is prepared by above-mentioned preparation method.
The present invention also provides a kind of foaming products, which is characterized in that including nanocomposite foaming agent, curing agent and asphalt mixtures modified by epoxy resin Rouge, the nanocomposite foaming agent are selected from above-mentioned nanocomposite foaming agent.
Preferably, in above-mentioned foaming product, the weight ratio of the nanocomposite foaming agent, curing agent and epoxy resin are as follows: (1-5): (4-10): 100, preferably (1-3): (4-10): 100.
Preferably, in above-mentioned foaming product, the curing agent is diethylenetriamine.
The present invention also provides a kind of epoxy resin microcellular foams, which is characterized in that by the mixing of above-mentioned foaming product, admittedly It is obtained after change.
Preferably, in above-mentioned epoxy resin microcellular foam, the temperature of the solidification process is 80-100 DEG C, preferably 80-90℃。
The present invention also provides above-mentioned nanocomposite foaming agent, application of the above-mentioned foaming product in foaming agent field.
The beneficial effects of the present invention are: in nanocomposite foaming agent of the present invention, the mesoporous silicon oxide of institute's reaming Mesopore orbit with super large, it is compatible with good interface to possess excellent dispersibility for modified mesoporous silicon oxide after institute's reaming Property, nanocomposite foaming agent agglomeration after institute's carrying out washing treatment be improved significantly.Therefore, by sending out chemistry in the present invention Infusion is introduced into ultra-large aperture and finely dispersed reaming, modified mesoporous silicon oxide in, and mitigated by carrying out washing treatment and received The reunion of rice composite foamable agent in the drying process, so that not only particle size is small for nanocomposite foaming agent provided by the invention, And to the loading of chemical foaming agent height, so as to obtain the better microcellular foam of foaming quality.
Detailed description of the invention
Fig. 1 is each modification described in reaming mesoporous silicon oxide (EMS4) described in the embodiment of the present invention 1.1 and embodiment 1.2 The infrared spectrogram of mesoporous silicon oxide (KH550-EMS4, KH560-EMS4 and KH570-EMS4).
Fig. 2 is each modification described in reaming mesoporous silicon oxide (EMS4) described in the embodiment of the present invention 1.1 and embodiment 1.2 Mesoporous silicon oxide (KH550-EMS4, KH560-EMS4 and KH570-EMS4) solid-state nuclear magnetic resonance cross-pole SiClx spectrum (29Si CP/MAS NMR) spectrogram.
Fig. 3-a, Fig. 3-b, Fig. 3-c and Fig. 3-d are respectively reaming mesoporous silicon oxide described in the embodiment of the present invention 1.1 (KH550-EMS4, amplification factor are modified mesoporous silicon oxide described in (EMS4, amplification factor 5000), embodiment 1.2 5000 times, KH560-EMS4, amplification factor are 5000 times and KH570-EMS4, and amplification factor is 5000 times) scanning electron it is aobvious Micro mirror (SEM) figure.
Fig. 4-a and Fig. 4-b is respectively the solid state nmr of KH550-EMS4 Yu nanocomposite foaming agent OBSH-KH550-EMS4 The cross-pole SiClx that resonates spectrum (29Si CP/MAS NMR) spectrogram.
Fig. 5 is the solid-state nuclear magnetic resonance cross polarization of KH550-EMS4 and nanocomposite foaming agent OBSH-KH550-EMS4 Carbon spectrum (13C CP/MAS NMR) spectrogram.
Fig. 6-a is of the gained sample F 2 after carrying out washing treatment of nanocomposite foaming agent described in the embodiment of the present invention 1.3 Scanning electron microscope (SEM) figure of grain size pattern.
Fig. 6-b is of the gained sample F 3 after carrying out washing treatment of nanocomposite foaming agent described in the embodiment of the present invention 1.3 Scanning electron microscope (SEM) figure of grain size pattern.
Fig. 6-c is of the gained sample F 1 after carrying out washing treatment of nanocomposite foaming agent described in the embodiment of the present invention 1.3 Scanning electron microscope (SEM) figure of grain size pattern.
Specific embodiment
In view of the combined efficiency of current composite foamable agent problem still to be improved, the present invention provides one kind with mesoporous dioxy Based on SiClx, using organic foaming agent as the nanocomposite foaming agent of object.
In a kind of preferred embodiment, the preparation process of nanocomposite foaming agent of the present invention is as follows:
It reacts to obtain mesoporous silicon oxide by sol-gal process, material of main part preparation is as follows: cetylamine is dissolved in isopropyl In alcohol solution (volume ratio 10:9), the ammonium hydroxide for being added 28% adjusts solution acid alkalinity as 7.5-11.5, is eventually adding positive silicic acid Ethyl ester, reacts 12-24h under certain temperature, and dehydrated alcohol rinses, centrifugation, calcining.Reaction temperature can be 20-45 DEG C, preferably 30℃。
The reaming mesoporous silicon oxide is obtained by above-mentioned mesoporous silicon oxide and alkali metal salt soln infusion process, system Standby process is as follows: above-mentioned mesoporous silicon oxide being dissolved in 23% alkali metal salt or the aqueous solution of double salt, is stirred evenly, is stood 3h is impregnated, is placed in 110 DEG C of baking ovens after 4h and is put into Muffle furnace calcining.Wherein, preferably lithium chloride, potassium nitrate or sodium chloride, chlorine Reaming can be played the role of by changing lithium and potassium nitrate double salt, and aperture adjustment range is 11.0nm-35.8nm.More preferably sodium chloride, The double salt of lithium chloride and potassium nitrate, reaming back aperture are 35.8nm.
The reaming, modified mesoporous silicon oxide are by above-mentioned reaming silica chemical modification, institute in example The material of main part preparation referred to is as follows: at a certain temperature, the mesoporous silicon oxide after above-mentioned double salt reaming being dissolved in ethanol water In solution, ultrasound, it is YRnSiX that a certain amount of general formula, which is added,3The silane coupling agent of (wherein n=1 or >=3), stirring for 24 hours, filter, It is dry.Wherein, the silane coupling agent dosage of the modified mesoporous silicon oxide of 1g can be 1-6mL, preferably 4mL；Reaction temperature Degree can be 25-60 DEG C, preferably 25 DEG C.
General formula is YRnSiX3The silane coupling agent of (wherein n=1 or >=3), wherein Y is organic compound functional group, packet Include-NH2、-HNCONH2、-HNCH2CH2NH2、-N3、Deng preferably-NH2,- HNCONH2,-HNCH2CH2NH2,-N3, further preferably-NH2、-HNCONH2, most preferably-NH2；X is hydrolysis functional group, packet Include-OCH3、-OCH2CH3、OCH2CH2OCH3,-Cl etc., preferably-OCH3、-OCH2CH3。
The nanocomposite foaming agent is impregnated by above-mentioned reaming, modified mesoporous silicon oxide and chemical foaming agent At the preparation of material of main part mentioned in example is as follows: under the conditions of existing for the organic solvent, chemical foaming agent being dissolved in organic In solvent, be stirring evenly and then adding into above-mentioned reaming, modified mesoporous silicon oxide, ultrasonic 10min, normal temperature dipping for 24 hours, gained sample It is washed with alcohol or alcohol mixing washing lotion, it is dry, the embedded nanocomposite foaming agent of meso-porous titanium dioxide silicon substrate is made.Wherein, it washs molten Agent includes but is not limited to methanol or the mixing washing lotion comprising methanol.
The present invention also provides the application that above-mentioned nanocomposite foaming agent prepares microcellular foam, mentioned in example Material of main part preparation is as follows:
Under certain temperature, a certain amount of above-mentioned nanocomposite foaming agent is added in 10g epoxy resin, is stirred evenly, A certain amount of curing agent diethylenetriamine is added, is quickly moved into after stirring in 80 DEG C of baking oven and continues solidification for 24 hours.Wherein, it reacts Temperature can be 80 DEG C -100 DEG C, preferably 80 DEG C；
Cleaning solvent includes but is not limited to methanol or the mixing washing lotion comprising methanol, preferably organic solvent, chemical blowing The near saturated solution of agent and methanol；The additional amount of nanocomposite foaming agent can be 0.1g-0.3g, preferably 0.2g；Curing agent Additional amount can be 0.5mL-0.7mL, preferably 0.6mL, to obtain epoxy resin microcellular foam.
Further illustrated below by specific embodiment nanocomposite foaming agent of the present invention and preparation method thereof and Using.
In the following embodiments, agents useful for same and facility information are as follows:
The double benzsulfamides of 4,4 '-oxos: lark prestige science and technology group.
Nitrogen adsorption-desorption curve: instrument: specific surface area and lacunarity analysis instrument, producer: Beijing Bi Aode electronic technology Co., Ltd, model: SSA-6000E.
Cell diameter and cell density measuring method: diameter is carried out using SEM figure of the Nano Measurer software to sample Measurement and number statistics, calculate mean cell diameter, further according to formula ρc=(Nm2/A)3/2Cell density is calculated, wherein for abscess Density (a/cm3), n is the abscess number (a) counted in area, and M is amplification factor, and A is statistics area (cm3)。
Nuclear Magnetic Resonance: producer: German Brooker company, model: Bruker AV300,13C MAS NMR test condition: Rotor speed 12kHz, relaxation delay time 10s, scanning times are 5000-7000 times, use glycine as chemical shift mark Quasi- reference material, the chemical shift of carbonyl carbon are 176.03ppm.
Scanning electron microscope: producer: FEI Co., the U.S., model: Quanta2050S is sticked to sample on sample stage with conducting resinl Metal spraying is handled afterwards, observes the pattern of powder sample.
The preparation of one nanocomposite foaming agent of embodiment
The reaming procedure of 1.1 mesoporous silicon oxide of embodiment
At 30 DEG C, 6g cetylamine is dissolved in 600mL isopropanol and 540mL water, the ammonia spirit of 8.4mL 28% is added, Adjusting pH is 11.2, and ethyl orthosilicate (TEOS) dropwise addition of 34.8mL is entered, and 30 DEG C stand one day, is rinsed with dehydrated alcohol, Programmed temperature method calcining preparation, obtains mesoporous silicon oxide MS；Described program temperature-raising method are as follows: (1) temperature is risen to 250 from room temperature DEG C, constant temperature 30min；(2) temperature is increased to 450 DEG C again, constant temperature 50min；(3) temperature is warming up to 600 DEG C again, constant temperature 4h.
Respectively prepare molar concentration be the NaCl solution of 5mol/L, the LiCl solution of 5mol/L, 5mol/L KNO3Solution, And mass ratio is NaCl, LiCl, KNO of 4:1:13Complex salt solution, and the mass fraction of complex salt solution be 23%.It will be on 2g It states mesoporous silicon oxide to be added separately in the above-mentioned four kinds of salting liquids of 100ml, stir evenly, impregnate 3h, put after 110 DEG C of drying 4h Enter Muffle furnace calcining.Calcining use programmed temperature method, temperature setting are as follows: from room temperature rise to 300 DEG C (heating rate be 10 DEG C/ Min), constant temperature 30min, this temperature range are that the combustion decomposition of water and organic impurities is adsorbed in nano particle, continue to heat up To 600 DEG C, (heating rate is 10 DEG C/min), stops heating after constant temperature 180min, takes out after natural cooling.After roasting reaming Mesoporous silicon oxide grinding after be added deionized water washing, millipore filter filter, wash up to no Cl-(0.lmol/mL's AgNO3Solution detection), it is put into baking oven, 80 DEG C of drying obtain reaming mesoporous silicon oxide, are denoted as EMS1, EMS2 respectively, EMS3, EMS4.
The modifying process of 1.2 reaming mesoporous silicon oxide of embodiment
The mesoporous silicon oxide EMS4 that 2g embodiment 1.1 obtains is added in 20ml water and 180ml alcohol mixed solution, Mechanical stirring is to uniform, ultrasonic 30min.It is added 4mL silane coupling agent gamma-aminopropyl-triethoxy-silane (KH550), magnetic force stirs It mixes for 24 hours, millipore filter filters, and it is dry, the modified mesoporous silicon oxide of KH550 is obtained, KH550-EMS4 is denoted as.
Similarly, above-mentioned silane coupling agent is changed to γ-glycidyl ether oxygen propyl trimethyl silane of same volume (KH560) or γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), under the same terms it is modified obtain KH560 and KH570 is modified mesoporous silicon oxide, is denoted as KH560-EMS4 and KH570-EMS4 respectively.
The preparation of 1.3 nanocomposite foaming agent of embodiment
The double benzsulfamides (OBSH) of 4,4 '-oxo of 2.69g chemical foaming agent are weighed, 15Ml N, N '-dimethyl formyl are dissolved in In amine (DMF), magnetic agitation is to uniform.The KH550-EMS4 for weighing the preparation of 0.5g embodiment 1.2 is added in above-mentioned solution, stirring Uniformly, ultrasonic 10min impregnates for 24 hours under room temperature, and millipore filter filters.With 10mL mixing washing lotion (the double benzene sulphurs of 2g 4,4 '-oxo Hydrazides, 10mL N, N ' dimethylformamide and 10mL methanol) washing after washed again with 10mL methanol, in 60 DEG C of baking ovens dry For 24 hours, nanocomposite foaming agent OBSH-KH550-EMS4 is obtained, F1 is denoted as.In the present embodiment, F1 refers to OBSH-KH550-EMS4 Generation is nanocomposite foaming agent of the same race.
Similarly, the mode of washing in the above method is changed to do not wash or 10mL methanol washing replace 10mL mix washing lotion It is washed again with 10mL methanol after (4,4 '-oxobenzenesulfonyl hydrazide of 2g, 10mL N, N ' dimethylformamide and 10mL methanol) washing It washs, the nanocomposite foaming agent obtained after washing is denoted as F2 respectively and is denoted as F3.
1.4 foaming product of embodiment
The present embodiment is for illustrating that nanocomposite foaming agent of the present invention is preparing the application in microcellular foam. At a certain temperature, being added to different mode of washing treated a certain amount of nanocomposite foaming agent in 10g epoxy resin, Normal pressure foaming experiment is carried out a certain amount of curing agent diethylenetriamine is added.Mode of washing (A), nanocomposite foaming agent are added Enter amount (B), blowing temperature (C) and curing agent additional amount (D) as 4 factors, 3 different states of each factor are as water It is flat, L9 (34) orthogonal design is carried out, orthonormal design of experiments is shown in Table 2.Wherein A1 is convection drying, and A2 is drying after methanol washing, A3 is above-mentioned mixing washing lotion (4,4 '-oxobenzenesulfonyl hydrazide of 2g, 10mL N, N ' dimethylformamide and 10mL methanol) washing Drying is washed with 10mL methanol again afterwards；B1 is 0.1 gram, and B2 is 0.2 gram, and B3 is 0.3 gram；C1 is 80 DEG C, and C2 is 90 DEG C, and C3 is 100℃；D1 is 0.5mL, and D2 is 0.6mL, and D3 is 0.7mL.
Table 1
In addition, following experiment of single factor are added in the present inventor:
Test 10:A2B2C1D3
Test 11:A1B2C1D3
Experiment 12: similar with 8 conditions of experiment, difference, which is only that, is changed to the component for mixing washing lotion: 4,4 '-oxo of 2g is double Benzsulfamide, 20ml methanol and 20ml N, N ' dimethylformamide.
Experiment 13: similar with 8 conditions of experiment, difference, which is only that, is changed to the component for mixing washing lotion: 4,4 '-oxo of 2g is double Benzsulfamide, 30ml methanol and 30ml N, N ' dimethylformamide.
The sample of embodiment 1.1-1.4 is subjected to following characterizations:
1. pore structure
MS, average pore size, Kong Rong and the specific surface area of EMS1, EMS2, EMS3 and EMS4 are detected respectively.Wherein nitrogen is inhaled Attached-desorption curve be using Beijing Bi Aode Electron Technology Co., Ltd production the full-automatic specific surface area of SSA-6000E type and Lacunarity analysis instrument is measured from, and according to Barrett-Joyner-Halenda (BJH) formula, passes through the suction in adsorption isotherm Fufen branch calculates average pore size and Kong Rong, specific surface area are calculated according to Brunauer-Emmett-Teller (BET) formula It arrives, as a result as shown in table 2 below.
Table 2
Sample ID Average pore size (nm) Kong Rong (cm3g-1) Specific surface area (m2·g-1)
MS 2.1 0.5 949.2
EMS1 2.1 0.5 886.8
EMS2 11.0 0.3 124.2
EMS3 20.4 0.3 52.9
EMS4 35.8 0.2 26.0
As shown in Table 2, MS and EMS1 due to micropore proportion it is larger, specific surface area is larger, in contrast, multiple The EMS4 average pore size obtained after salt dipping is closed up to 35.8nm, reaming effect is relatively more preferable.
2. infrared detection
The material (KH550-EMS4, KH560-EMS4 and KH570-EMS4) prepared respectively to EMS4, embodiment 1.2 carries out Infrared spectrum analysis, their own FTIR spectrum are as shown in Figure 1.
It will be seen from figure 1 that characteristic absorption peak (the 1093cm of Si-O-Si key-1) by modified all obvious broadening, this is to change Characteristic absorption peak (the 1167cm of the Si-O-C generated after property-1, 1107cm-1And 1075cm-1) with the characteristic absorption of Si-O-Si key Caused by peak is superimposed.And KH550 is modified in 1560cm-1There is the bending vibration characteristic absorption peak of N-H in KH550 in place, KH560 is modified in 2944cm-1There is the characteristic absorption peak of methylene in place, and KH570 is modified in 1719cm-1There is C in place The characteristic absorption peak of=O.Thus illustrate, mesoporous silicon oxide is successfully modified by KH550, KH560 and KH570.
3. nuclear magnetic resonance
The material (KH550-EMS4, KH560-EMS4 and KH570-EMS4) prepared respectively to EMS4, embodiment 1.2 carries out Solid-state nuclear magnetic resonance cross-pole SiClx spectrum (29Si CP/MAS NMR) analysis, it is their own29Si CP/MAS NMR spectra is such as Shown in Fig. 2.
Figure it is seen that EMS4 only exists Q structural unit, and it is modified, it generates silicon atom and is connected with organic group S structural unit.Thus illustrate, mesoporous silicon oxide is successfully modified by KH550, KH560 and KH570.
4. scanning electron microscope analysis
The material (KH550-EMS4, KH560-EMS4 and KH570-EMS4) prepared respectively to EMS4, embodiment 1.2 carries out Scanning electron microscope (SEM) analysis, their own SEM figure is as shown in Fig. 3-a to Fig. 3-d.
From figure 3, it can be seen that EMS4 average diameter is about 800nm, but there are many aggregates for being greater than 5 μm.KH550- EMS4 particle shows a monodisperse distribution substantially, and there is only 2 μm of minute quantity or so of aggregate, KH570-EMS4 to exist by KH560-EMS4 2 μm to 4 μm a small amount of of aggregate.Thus illustrate, modification reduces reunion, improves dispersion.
Wherein, the partial size of EMS4 and modified mesoporous silicon oxide is up to 0.4-1.2 μm.
5. nuclear magnetic resonance
To embodiment 1.3 prepare foaming agent F1 carry out solid-state nuclear magnetic resonance cross-pole SiClx spectrum (29Si CP/MAS NMR) Analysis, KH550-EMS4 and F1's (i.e. OBSH-KH550-EMS4)29Si CP/MAS NMR spectra is as shown in Fig. 4-a to Fig. 4-b.
It can be seen that compared with KH550-EMS4 from Fig. 4-a and Fig. 4-b, the S structural unit content of F1 reduces, Q structure list First content increases.Thus illustrate, chemical foaming agent has entered in the duct of KH550-EMS4, and chemical foaming agent is to Q structural unit Polarization enhancing.
6. nuclear magnetic resonance
To embodiment 1.3 prepare foaming agent F1 carry out solid-state nuclear magnetic resonance cross polarization carbon spectrum (13C CP/MAS NMR) Analysis, KH550-EMS4 and F1's (i.e. OBSH-KH550-EMS4)13C CP/MAS NMR spectra is as shown in Figure 5.
From fig. 5, it can be seen that compared with KH550-EMS4, F1's13There is apparentization on C CP/MAS NMR spectra The characteristic absorption peak (100-170ppm) for learning foaming agent (OBSH), with OBSH's pure in document13C CP/MAS NMR spectra is compared, Phenyl ring limitation of movement in OBSH, the spectral peak at phenyl ring broaden.Thus illustrate, chemical foaming agent is successfully supported into KH550- In the duct of EMS4.
7. scanning electron microscope analysis
The foaming agent F1-F3 prepared respectively to embodiment 1.3 is scanned electron microscope (SEM) analysis, F2, F3 and F1 SEM figure respectively as shown in Fig. 6-a, Fig. 6-b and Fig. 6-c, the F1 partial size known to figure detection is 0.4-6.5 μm, and F3 partial size is 0.4-1μm。
From Fig. 6-a to Fig. 6 ,-c can be seen that different mode of washing and be dispersed with very big shadow to nanocomposite foaming agent It rings.The solvent DMF polarity used during preparing nanocomposite foaming agent is larger, is removed using the lesser solvent of polarity Re-dry facilitates the dispersion of nanocomposite foaming agent after DMF, is washed using the near saturated solution of chemical foaming agent, removes DMF While can also slow down chemical foaming agent in interpore precipitation, it helps nanocomposite foaming agent preferably disperses.
8. scanning electron microscope analysis
The foamed material prepared respectively to embodiment 1.4 is scanned electron microscope (SEM) analysis, utilizes Nano Measure software is for statistical analysis by above-mentioned SEM figure, as a result as shown in table 3 below.From table 3 it can be seen that by the nanometer of preparation Composite foamable agent, which is added in epoxy resin, carries out normal pressure foaming, and the foaming condition of optimization is A3B2C1D3, the asphalt mixtures modified by epoxy resin of preparation Fat vacuole foam plastics mean cell diameter is 34.4 μm, and cell density is 1.3 × 106A/cm3。
Table 3
Embodiment two
Embodiment two is similar to the preparation process of embodiment one, and difference is only that: (1) in the preparation of nanocomposite foaming agent In the process, the quality of OBSH is changed to 1.5g；Washing process are as follows: with 10mL mixing washing lotion (4,4 '-oxobenzenesulfonyl hydrazide of 2g, 10mL N, N ' dimethylformamide and 10mL methanol) washing after washed again with 10mL methanol, in 60 DEG C of baking ovens dry for 24 hours, obtain Nanocomposite foaming agent.
It is tested after 8 identical foaming methods foam to epoxy resin and can be obtained with embodiment one, 50 μm of aperture < Abscess percentage is 80.3%, and mean cell diameter is 38.9 μm, and cell density is 9.7 × 105A/cm3。
Embodiment three
Embodiment three is similar to the preparation process of embodiment one, and difference is only that: by the preparation of nanocomposite foaming agent The quality of OBSH is changed to 3.5g in journey；Washing process are as follows: mix washing lotion (4,4 '-oxobenzenesulfonyl hydrazide of 2g, 10mL with 10mL N, N ' dimethylformamide and 10mL methanol) washing after washed again with 10mL methanol, in 60 DEG C of baking ovens dry for 24 hours, obtain nanometer Composite foamable agent.
It is tested after 8 identical foaming methods foam to epoxy resin and can be obtained with embodiment one, 50 μm of aperture < Abscess percentage is 72.6%, and mean cell diameter is 42.7 μm, and cell density is 7.8 × 105A/cm3。
Example IV
Example IV is similar to the preparation process of embodiment one, and difference is only that: double salt used is that mass ratio is 4:1:1's NaCl、LiCl、KNO3Complex salt solution, and the mass fraction of complex salt solution be 5%.
Washing process are as follows: mix washing lotion (4,4 '-oxobenzenesulfonyl hydrazide of 2g, 10mL N, N ' dimethyl formyl with 10mL Amine and 10mL methanol) washing after washed again with 10mL methanol, in 60 DEG C of baking ovens dry for 24 hours, obtain nanocomposite foaming agent.
It is tested after 8 identical foaming methods foam to epoxy resin and can be obtained with embodiment one, 50 μm of aperture < Abscess percentage is 76.2%, and mean cell diameter is 36.5 μm, and cell density is 6.7 × 105A/cm3。
Embodiment five
Embodiment five is similar to the preparation process of embodiment one, and difference is only that: double salt used is that mass ratio is 4:1:1's NaCl、LiCl、KNO3Complex salt solution, and the mass fraction of complex salt solution be 70%.
Washing process are as follows: mix washing lotion (4,4 '-oxobenzenesulfonyl hydrazide of 2g, 10mL N, N ' dimethyl formyl with 10mL Amine and 10mL methanol) washing after washed again with 10mL methanol, in 60 DEG C of baking ovens dry for 24 hours, obtain nanocomposite foaming agent.
It is tested after 8 identical foaming methods foam to epoxy resin and can be obtained with embodiment one, 50 μm of aperture < Abscess percentage is 67.4%, and mean cell diameter is 47.1 μm, and cell density is 7.2 × 105A/cm3。
Comparative example one
Comparative example one is similar to the preparation process of embodiment one, and difference is only that: by 1.2 reaming meso-porous titanium dioxide of embodiment EMS4 used in the modifying process of silicon is changed to not be the mesoporous silicon oxide MS of expanding treatment.
It is tested after 8 identical foaming methods foam to epoxy resin and can be obtained with embodiment one, 50 μm of aperture < Abscess percentage is 77.8%, and mean cell diameter is 39.5 μm, and cell density is 3.3 × 105A/cm3。
Comparative example two
Comparative example two is similar to the preparation process of embodiment one, and difference is only that: double salt used is that mass ratio is 4:1:1's NaCl、LiCl、KNO3Complex salt solution, and the mass fraction of complex salt solution be 80%.
Washing process are as follows: mix washing lotion (4,4 '-oxobenzenesulfonyl hydrazide of 2g, 10mL N, N ' dimethyl formyl with 10mL Amine and 10mL methanol) washing after washed again with 10mL methanol, in 60 DEG C of baking ovens dry for 24 hours, obtain nanocomposite foaming agent.
It is tested after 8 identical foaming methods foam to epoxy resin and can be obtained with embodiment one, 50 μm of aperture < Abscess percentage is 50.6%, and mean cell diameter is 53.2 μm, and cell density is 4.5 × 105A/cm3。
In conclusion successfully being introduced chemical foaming agent by preparation method of the present invention has large aperture and is uniformly dispersed Modification mesoporous silicon oxide in, not only particle size is small for nanocomposite foaming agent obtained, and supports to chemical foaming agent Amount is high, and microcellular foam cell density obtained is big, functional, is with a wide range of applications.

Claims (24)

1. a kind of preparation method of nanocomposite foaming agent, it is characterised in that: mesoporous silicon oxide is successively passed through to reaming and is connect Branch is modified, obtains modified mesoporous silicon oxide；Will modified mesoporous silicon oxide with 4,4 '-oxobenzenesulfonyl hydrazide are compound obtains Nanocomposite foaming agent, wherein the modified mesoporous silicon oxide and 4, the mass ratio of 4 '-oxobenzenesulfonyl hydrazide are 1:(3- 7),
Wherein, the preparation method of the nanocomposite foaming agent includes the following steps:
(1) expanding treatment is carried out to mesoporous silicon oxide with salt impregnation method；
(2) mesoporous silicon oxide after reaming is added in modifying agent and is modified, obtain modified mesoporous silicon oxide；
(3) N of 4,4 '-oxobenzenesulfonyl hydrazide will be contained, above-mentioned modified meso-porous titanium dioxide is added in N '-dimethyl formamide solution In silicon, successively after ultrasound, washing, nanocomposite foaming agent is obtained；
Wherein, the cleaning solvent is methanol or including methanol, 4,4 '-oxobenzenesulfonyl hydrazide and N, N '-dimethyl formamide Mixing washing lotion.
2. preparation method according to claim 1, wherein the salt used in salt impregnation method described in step (1) includes one The mixture of kind or two or more alkali metal salts；The mass concentration of the salt is 5-70%.
3. preparation method according to claim 2, wherein the mass concentration of the salt is 20-30%.
4. preparation method according to claim 2, wherein the alkali metal salt is sodium chloride, lithium chloride or potassium nitrate The double salt of one or more composition.
5. preparation method according to claim 1-4, wherein the process packet of expanding treatment described in step (1) Include following step:
After salting liquid is added in mesoporous silicon oxide, calcined with programmed temperature method, described program temperature-rise period includes following Step:
(1) temperature is risen into the first calcination temperature, constant temperature 30-60min from room temperature；
(2) temperature is warming up to the second calcination temperature, constant temperature 3-5h from the first calcination temperature；
Wherein, first calcination temperature is 200-300 DEG C, and the second calcination temperature is 400-700 DEG C.
6. preparation method according to claim 5, wherein the ratio of the mesoporous silicon oxide and salting liquid is 1g: (0.1-100)ml。
7. preparation method according to claim 1-4, wherein the preparation process of the mesoporous silicon oxide includes Following step:
Ethyl orthosilicate is added in the organic solvent containing cetylamine, calcining obtains mesoporous silicon oxide；The positive silicic acid second The ratio of ester and cetylamine is (30-40) ml:(5-7) g.
8. preparation method according to claim 1-4, wherein the modifying agent is silane coupling agent.
9. preparation method according to claim 1-4, wherein the modifying agent is gamma-aminopropyl-triethoxy Silane, γ-glycidyl ether oxygen propyl trimethyl silane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
10. preparation method according to claim 5, wherein the modifying agent is gamma-aminopropyl-triethoxy-silane, γ- Glycidyl ether oxygen propyl trimethyl silane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
11. preparation method according to claim 6, wherein the modifying agent is gamma-aminopropyl-triethoxy-silane, γ- Glycidyl ether oxygen propyl trimethyl silane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
12. preparation method according to claim 7, wherein the modifying agent is gamma-aminopropyl-triethoxy-silane, γ- Glycidyl ether oxygen propyl trimethyl silane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
13. preparation method according to claim 1-4, wherein it is double to contain 4,4 '-oxos described in step (3) The N of benzene sulfonyl hydrazide, in N '-dimethyl formamide solution, the concentration of 4,4 '-oxobenzenesulfonyl hydrazide is 0.2mo/L~0.5mol/ L。
14. preparation method according to claim 13, wherein described 4, the concentration of 4 '-oxobenzenesulfonyl hydrazide is 0.4- 0.5mol/L。
15. preparation method according to claim 1-4, wherein the washing process includes the following steps:
(1) it is washed with mixing washing lotion；
(2) again with methanol is washed；
Wherein, the mixing washing lotion includes methanol, 4,4 '-oxobenzenesulfonyl hydrazide and N, N '-dimethyl formamide.
16. preparation method according to claim 9, wherein the washing process includes the following steps:
(1) it is washed with mixing washing lotion；
(2) again with methanol is washed；
Wherein, the mixing washing lotion includes methanol, 4,4 '-oxobenzenesulfonyl hydrazide and N, N '-dimethyl formamide.
17. preparation method according to claim 15, wherein in the mixing washing lotion, with the double benzene sulphurs of every gram of 4,4 '-oxos Hydrazides meter, the N of methanol and 5-15ml including 5-15ml, N '-dimethyl formamide.
18. preparation method according to claim 15, wherein in the mixing washing lotion, with the double benzene sulphurs of every gram of 4,4 '-oxos Hydrazides meter, the N of methanol and 5-10ml including 5-10ml, N '-dimethyl formamide.
19. a kind of nanocomposite foaming agent, which is characterized in that be prepared by any one of the claim 1-18 preparation method It arrives.
20. a kind of foaming product, which is characterized in that including nanocomposite foaming agent, curing agent and epoxy resin, the nanometer is multiple It closes foaming agent and is selected from nanocomposite foaming agent described in claim 19.
21. the foaming product according to claim 20, wherein the nanocomposite foaming agent, curing agent and epoxy resin Weight ratio are as follows: (1-5): (4-10): 100.
22. the foaming product according to claim 20, wherein the nanocomposite foaming agent, curing agent and epoxy resin Weight ratio is (1-3): (4-10): 100.
23. a kind of epoxy resin microcellular foam, which is characterized in that by any one of the claim 20-22 foaming product It is obtained after mixing, solidification.
24. any one of nanocomposite foaming agent described in claim 19 or claim the 20-22 foaming product are foaming The application in agent field.
CN201610333686.5A 2016-05-19 2016-05-19 Nanocomposite foaming agent, foaming product and its preparation method and application Active CN105949720B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610333686.5A CN105949720B (en) 2016-05-19 2016-05-19 Nanocomposite foaming agent, foaming product and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610333686.5A CN105949720B (en) 2016-05-19 2016-05-19 Nanocomposite foaming agent, foaming product and its preparation method and application

Publications (2)

Publication Number Publication Date
CN105949720A CN105949720A (en) 2016-09-21
CN105949720B true CN105949720B (en) 2019-05-03

Family

ID=56912076

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610333686.5A Active CN105949720B (en) 2016-05-19 2016-05-19 Nanocomposite foaming agent, foaming product and its preparation method and application

Country Status (1)

Country Link
CN (1) CN105949720B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106566050A (en) * 2016-10-31 2017-04-19 江苏昊晟塑业科技有限公司 A foaming material used for automobile interior trim
CN107022102B (en) * 2017-04-27 2022-12-13 北京化工大学 Preparation method of monodisperse mesoporous silica, nano composite foaming agent, preparation method and application
CN112126197A (en) * 2020-09-30 2020-12-25 贵州凯科特材料有限公司 Preparation method of alternating multilayer epoxy resin-based conductive composite microporous foam material
CN112679788A (en) * 2021-01-26 2021-04-20 江苏威久科技发展有限公司 Nano composite foaming agent for preparing polyurethane and preparation method thereof
CN113975454A (en) * 2021-11-12 2022-01-28 延边大学 Preparation and application of mesoporous silica/tannic acid composite hydrogel hemostatic material
CN114409951B (en) * 2021-12-31 2023-07-28 北京化工大学 Monodisperse composite foaming agent, microbubble plastic and preparation method thereof
CN114479158B (en) * 2022-03-16 2023-10-27 青岛科技大学 High-dispersion foaming agent and preparation method of composite foaming agent thereof
CN116351399A (en) * 2022-12-30 2023-06-30 厦门色谱分析仪器有限公司 Bonding cellulose derivative chiral liquid chromatographic column and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101274999A (en) * 2007-03-30 2008-10-01 北京化工大学 Novel composite vesicant
CN102250375A (en) * 2010-05-19 2011-11-23 北京化工大学 Preparation method for nano-composite foaming agent based on porous inorganic material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101274999A (en) * 2007-03-30 2008-10-01 北京化工大学 Novel composite vesicant
CN102250375A (en) * 2010-05-19 2011-11-23 北京化工大学 Preparation method for nano-composite foaming agent based on porous inorganic material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"基于介孔二氧化硅微球的OBSH复合发泡剂的组装";王梅;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20100115(第01期);第B020-481页

Also Published As

Publication number Publication date
CN105949720A (en) 2016-09-21

Similar Documents

Publication Publication Date Title
CN105949720B (en) Nanocomposite foaming agent, foaming product and its preparation method and application
CN103738969B (en) Mesoporous silica and preparation method thereof
CN104556072B (en) A kind of in-situ modified method preparing monodisperse nano silicon dioxide
CN106044788A (en) Nanometer material with controllable particle sizes and silicon dioxide hollow spheres and method for preparing nanometer material
CN103205013B (en) Polymer supercritical carbon dioxide foaming nucleating agent and preparation method and application thereof
Ge et al. Synthesis of porous hollow silica spheres using polystyrene–methyl acrylic acid latex template at different temperatures
CN110203938A (en) A kind of method and its application preparing multi-stage porous silicon dioxide ultrafine powder body for template based on glucan
TW201641544A (en) Aerogel granule and preparation method thereof
CN108579705A (en) A kind of preparation method of mesoporous silicon dioxide micro-sphere
CN114409951B (en) Monodisperse composite foaming agent, microbubble plastic and preparation method thereof
CN102515173A (en) Method for preparing mesoporous SBA-15 unstuck micro spheres
CN106745007A (en) A kind of multi-stage porous mesoporous organosilicon ball and preparation method thereof
CN114436272A (en) Mesoporous silica nanosheet with high specific surface area and preparation method thereof
CN102020283A (en) Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter
Li et al. Newly designed copolymers for fabricating particles with highly porous architectures
Velikova et al. Synthesis and characterization of sol–gel mesoporous organosilicas functionalized with amine groups
CN107022102A (en) Monodisperse mesoporous silica preparation method and nanocomposite foaming agent, preparation method and application
CN104485191A (en) Magnetic hollow nanometer ball and preparation method thereof
CN104746178A (en) Preparation method of silicate double-layer hollow nanometer fiber with multistage structure
Wang et al. Preparation of hierarchically mesoporous silica microspheres with ordered mesochannels and ultra-large intra-particulate pores
CN111569797A (en) Inverse opal type macroporous/mesoporous nitrogen-doped carbon microsphere and preparation method thereof
CN104891510A (en) Method for preparing millimeter SiO2 aerogel ball by drying under normal pressure
CN103601201B (en) Monodisperse mesoporous monox nanometer particle and synthetic method thereof
CN104592430B (en) Ultrahigh molecular weight polyethylene catalyst carrier material and preparation method thereof
Li et al. Templating amphiphilic poly (ethylene oxide-b-ε-caprolactone) diblock copolymers provides ordered mesoporous silicas with large tunable pores

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant