CN105949720A - Nano composite foaming agent, foaming product, and preparation method and application thereof - Google Patents

Nano composite foaming agent, foaming product, and preparation method and application thereof Download PDF

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Publication number
CN105949720A
CN105949720A CN201610333686.5A CN201610333686A CN105949720A CN 105949720 A CN105949720 A CN 105949720A CN 201610333686 A CN201610333686 A CN 201610333686A CN 105949720 A CN105949720 A CN 105949720A
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foaming agent
silicon oxide
preparation
mesoporous silicon
nanocomposite
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CN105949720B (en
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郭灿雄
王足远
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • 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

Abstract

The invention relates to the field of foaming agents, in particular to a nano composite foaming agent, a foaming product, and a preparation method and application thereof. The nano composite foaming agent is characterized in that the nano composite foaming agent is formed by compounding modified mesoporous silica and 4,4'-oxobibenzene sulfonamide, the mass ratio of the modified mesoporous silica to the 4,4'-oxobibenzene sulfonamide is 1: (3-7), and the modified mesoporous silica is obtained by successively carrying out pore expanding and grafted modification on the mesoporous silica. The nano composite foaming agent not only is small in particle size, but also is high in loading amount on a chemical foaming agent, so that micropore foamed plastic with good foaming quality can be obtained, and the application prospect is wide.

Description

Nanocomposite foaming agent, foaming product and preparation method thereof and application
Technical field
The present invention relates to foaming agent field, relate generally to composite foamable agent field, be specifically related to nano combined Infusion, foaming product and preparation method thereof and application.
Background technology
Mesoporous nano composite is to be filled into nano-particle or cluster to have institute in the space of meso-scale The complex formed, due to confinement effect and interface coupling effect, the Mesoporous Composites of this heterogeneous out-phase Have and be not only different from nano-particle but also be different from the property of common mesoporous material itself.Mesoporous silicon oxide Material has bigger specific surface area and pore volume, and aperture and pattern have adjustable degeneration, are increasingly becoming and receive Carrier material the most frequently used in rice mesoporous composite material.
Microcellular foam refers to that uniformly and cell diameter is less than the foam plastics of 100 μm in distribution of cells, Typical cellular plastic abscess cell diameter is 5～50 μm, and cell density reaches 109～1012Individual/cm3.Micropore Foam plastics is a kind of novel light material, and its design concept is that utilization is dispersed in polymeric matrix Fine and close and minimum abscess, these small cells are less than the intrinsic gap of plastics itself or little defect, play The effect that stress is concentrated, creates multiple crazing, has been passivated crack tip, slow down crack growth, make Microcellular foam has the heat stability more excellent than conventional foams and mechanical property, lower Dielectric constant and preferably insulating properties.
At present, preparing the foaming agent that foam plastics used mainly has two classes, a class to be physical blowing agents, and one Class is CBA.Use physical blowing agent to prepare microcellular foam to generally include monomer polymerization method, surpass Critical fluids precipitation method, heat guide phase separation method and supersaturated gas method, and most common of which is shooting flow Body precipitation method, but with CO2For represent supercritical fluid physical blowing agent dissolubility in the polymer low, The feature that diffusibility is high makes the abscess pattern of control foamed plastic extremely difficult, and equipment joint cost is high, institute The experiment condition such as drastically blood pressure lowering or intensification etc. needed is not easily accomplished, a large amount of production micropore plastic products or difficulty Point.Using CBA method when preparing foam plastics, CBA cannot be due to electrostatic agglomeration effect In polymer dispersed, and foaming process lacks nucleating point, and foaming quality is poor, it is difficult to obtain fine-celled foam Plastics.
It is multiple that patent (Application No. 201010176081.2) provides a kind of nanometer based on porous inorganic material Close foaming agent: after being modified by porous inorganic material, the object of composite foamable agent is dissolved in certain quantitative In solvent, it is combined with modified porous inorganic material, multiple through separating, be dried prepared nanometer after a period of time Close foaming agent.Although this patent can solve the problem that foaming agent is reunited, but its organic foaming to a certain extent The space that agent object load capacity on porous inorganic material is still improved, the foaming of its nanocomposite foaming agent Efficiency still has much room for improvement.
Patent (Application No. 201410051937.1) provides a kind of nanocomposite foaming agent: stratiform covered After de-soil is peeled off, by it with 4, the restructuring of 4-OBSH is compound, but stratiform montmorillonite due to The foaming agent that its architectural feature makes interlayer load is easier to by solvent eluting, nano combined prepared Infusion particle size is relatively big, and distribution is uniform not, and its character still has much room for improvement.
Summary of the invention
Present invention solves the technical problem that and be: although existing composite foamable agent can solve abscess to a certain extent The unmanageable problem of size, but the composite effect of foaming agent still has much room for improvement, on composite foamable agent at present Nucleating point still has to be increased, and bubbling efficiency and quality need to improve further.
It is an object of the invention to: based on silicon dioxide, it is provided that a kind of nanocomposite foaming agent, by right Silicon dioxide carries out reaming and modification, is optimized the combination process of silicon dioxide and organic foaming agent, from And improve combined efficiency, improve bubbling efficiency and quality further.
For solving above-mentioned technical problem, the invention provides a kind of nanocomposite foaming agent, wherein, described in receive Rice composite foamable agent contains CBA and sequentially passes through reaming, modified mesoporous silicon oxide (MS), Described reaming silicon dioxide forms by being impregnated with alkali metal salt or double salt by silicon dioxide, described modification Reaming silicon dioxide is by being YRnSiX by reaming silicon dioxide and formula3Silane coupler reaction and make , wherein Y is organic compound functional group, and R is methylene or phenyl, and X is hydrolyzable functional group.
Present invention also offers the preparation method of a kind of nanocomposite foaming agent, the method includes: organic molten Under conditions of agent exists, mix with CBA connect sequentially passing through reaming, modified mesoporous silicon oxide The most fully washing, described reaming silicon dioxide is by impregnating silicon dioxide and alkali metal salt or double salt Becoming, described modified reaming silicon dioxide is by being YRnSiX by reaming silicon dioxide and formula3(wherein N=1 or >=3) silane coupler reaction prepare, wherein Y is organic compound functional group, and R is methylene Base or phenyl, X is hydrolyzable functional group, and described cleaning solvent includes the mixed solution of alcohol and alcohol.
In the present invention, term " mesoporous " refers to that average pore diameter is the hole between 2-50 nanometer, the most just It is to say that mesoporous material refers to average pore diameter material between 2 nanometers and 50 nanometers；" nanometer is multiple for term Close " refer to that filling in composite is the most one-dimensional there is nanoscale, bag expands nano-particle in the form of sheets Structure, the most one-dimensional in nanoscale, nano-particle is bar-shaped, and bidimensional is in nanoscale and nanometer Grain is in chondritic, three-dimensional all in nanoscale.In the third material, also include that particle size is micro- Meter level, but hole dimension is nano level spheroidal particle.
Present invention also offers that above-mentioned nanocomposite foaming agent prepares foaming product and microcellular foam should With.
Specifically, for the deficiencies in the prior art, the technical scheme is that
A kind of nanocomposite foaming agent, it is characterised in that by modified mesoporous silicon oxide and 4,4 '-oxo is double Benzsulfamide is composited, described modified mesoporous silicon oxide and 4, the mass ratio of the double benzsulfamide of 4 '-oxo For 1:(3-7)；Wherein, described modified mesoporous silicon oxide is to be sequentially passed through reaming by mesoporous silicon oxide Obtain with after graft modification.
Preferably, in above-mentioned nanocomposite foaming agent, described modified mesoporous silicon oxide and 4,4 '-oxo is double The mass ratio of benzsulfamide is 1:(4-6).
Preferably, in above-mentioned nanocomposite foaming agent, the particle diameter of described nanocomposite foaming agent is 0.8-10 μ M, preferably 0.4-6.5 μm, more preferably 0.4-1 μm.
Preferably, in above-mentioned nanocomposite foaming agent, the aperture of described mesoporous silicon oxide is 2-40nm, It is preferably 10-36nm.
Preferably, in above-mentioned nanocomposite foaming agent, the particle diameter of described mesoporous silicon oxide is 0.1-2 μm, It is preferably 0.4-1.5 μm.
The present invention also provides for the preparation method of above-mentioned nanocomposite foaming agent, it is characterised in that: to mesoporous dioxy After SiClx sequentially passes through reaming and graft modification, obtain modified mesoporous silicon oxide；By modification meso-porous titanium dioxide Silicon and 4, the double benzsulfamide of 4 '-oxo is compound obtains nanocomposite foaming agent, wherein, described modification mesoporous two The mass ratio of silicon oxide and the double benzsulfamide of 4,4 '-oxo is 1:(3-7).
Preferably, in above-mentioned preparation method, the preparation method of described nanocomposite foaming agent comprises the steps:
(1) with salt impregnation method, mesoporous silicon oxide is carried out expanding treatment；
(2) by the mesoporous silicon oxide addition modifying agent after reaming is modified, modified mesoporous two are obtained Silicon oxide；
(3) above-mentioned changing will be added containing the N of the double benzsulfamide of 4,4 '-oxo, N '-dimethyl formamide solution Property mesoporous silicon oxide in, sequentially pass through ultrasonic, washing after, obtain nanocomposite foaming agent.
Preferably, in above-mentioned preparation method, the preparation method of described nanocomposite foaming agent includes following Step:
(1) with salt impregnation method, mesoporous silicon oxide is carried out expanding treatment；
(2) mesoporous silicon oxide after reaming is scattered in ethanol water, sonicated after, add Enter in modifying agent and be modified, obtain modified mesoporous silicon oxide；
(3) dimethyl formamide solution containing the double benzsulfamide of 4,4 '-oxo is added above-mentioned modification mesoporous In silicon dioxide, sequentially pass through ultrasonic, washing after, obtain nanocomposite foaming agent.
Preferably, in above-mentioned preparation method, the salt used in salt impregnation method described in step (1) includes one Plant or the mixture of two or more alkali metal salt；The mass concentration of described alkali metal salt is 5-70%, is preferably 20-30%.
Preferably, in above-mentioned preparation method, described alkali metal salt is the one of sodium chloride, lithium chloride or potassium nitrate Plant or the double salt of two or more composition.
Preferably, in above-mentioned preparation method, the mass ratio of described double salt is: sodium chloride: lithium chloride: nitric acid Sodium=(3-5): 1:1.
Preferably, in above-mentioned preparation method, described in step (1), the process of expanding treatment includes following step Rapid:
After mesoporous silicon oxide is added saline solution, calcine with programmed temperature method, described temperature programming Journey comprises the steps:
(1) temperature is risen to the first calcining heat, constant temperature 30-60min from room temperature；
(2) temperature is warming up to the second calcining heat, constant temperature 3-5h from the first calcining heat；
Wherein, described first calcining heat is 200-300 DEG C, and the second calcining heat is 400-700 DEG C.
Preferably, in above-mentioned preparation method, described mesoporous silicon oxide is 1g with the ratio of saline solution: (0.1-100)ml。
Preferably, in above-mentioned preparation method, described mesoporous silicon oxide with the dip time of saline solution is 3-24h。
Preferably, in above-mentioned preparation method, the preparation process of described mesoporous silicon oxide comprises the steps:
Being added by tetraethyl orthosilicate in the organic solvent containing cetylamine, calcining obtains mesoporous silicon oxide；Institute The ratio stating tetraethyl orthosilicate and cetylamine is (30-40) ml:(5-7) g.
Preferably, in above-mentioned preparation method, described calcination process is Temperature Programmed Processes, comprises the steps:
(1) temperature is risen to the first calcining heat, constant temperature 30-60min from room temperature.
(2) temperature is warming up to the second calcining heat, constant temperature 30-60min from the first calcining heat.
(3) temperature is warming up to the 3rd calcining heat, constant temperature 3-5h from the second calcining heat.
Wherein, described first calcining heat is 200-300 DEG C, and the second calcining heat is 400-500 DEG C, the Three calcining heats are 600-800 DEG C.
Preferably, in above-mentioned preparation method, described modifying agent is silane coupler, preferably γ-aminopropyl three Ethoxysilane, γ-glycidyl ether oxygen propyl trimethyl silane or γ-(methacryloxypropyl) propyl group front three TMOS.
Preferably, in above-mentioned preparation method, described silane coupler is (1-6) with the ratio of mesoporous silicon oxide Ml:1g, is preferably (4-6) ml:1g.
Preferably, in above-mentioned preparation method, described modification temperature is 25-60 DEG C, preferably 25 DEG C.
Preferably, in above-mentioned preparation method, containing 4 described in step (3), the double benzsulfamide of 4 '-oxo N, in N '-dimethyl formamide solution, 4, the concentration of the double benzsulfamide of 4 '-oxo is 0.2mo/L～0.5mol/L, It is preferably 0.4-0.5mol/L.
Preferably, in above-mentioned preparation method, in step (2) and step (3), ultrasonic time is 10-30min.
Preferably, in above-mentioned preparation method, described in step (3), washing liquid used by washing process includes methanol.
Preferably, in above-mentioned preparation method, described washing process comprises the steps:
(1) wash by mixing washing liquid；
(2) wash with methanol；
Wherein, described mixing washing liquid include methanol, 4, the double benzsulfamide of 4 '-oxo and N, N '-dimethyl formyl Amine.
Preferably, in above-mentioned preparation method, in described mixing washing liquid, with every gram 4, the double benzene sulfonyl of 4 '-oxo Amine meter, including methanol and the N of 5-15ml of 5-15ml, N '-dimethyl Methanamide, preferably 5-10ml Methanol and the N of 5-10ml, N '-dimethyl Methanamide.
The present invention also provides for a kind of nanocomposite foaming agent, it is characterised in that prepared by above-mentioned preparation method Obtain.
The present invention also provides for a kind of foaming product, it is characterised in that include nanocomposite foaming agent, firming agent And epoxy resin, described nanocomposite foaming agent is selected from above-mentioned nanocomposite foaming agent.
Preferably, in above-mentioned foaming product, the weight of described nanocomposite foaming agent, firming agent and epoxy resin Amount ratio is: (1-5): (4-10): 100, is preferably (1-3): (4-10): 100.
Preferably, in above-mentioned foaming product, described firming agent is diethylenetriamine.
The present invention also provides for a kind of epoxy resin microcellular foam, it is characterised in that by above-mentioned foaming product Obtain after mixing, solidification.
Preferably, in above-mentioned epoxy resin microcellular foam, the temperature of described solidification process is 80-100 DEG C, preferably 80-90 DEG C.
The present invention also provides for above-mentioned nanocomposite foaming agent, and above-mentioned foaming product is in the application in foaming agent field.
The invention has the beneficial effects as follows: in nanocomposite foaming agent of the present invention, mesoporous the two of institute's reaming Silicon oxide has the mesopore orbit of super large, and the mesoporous silicon oxide of institute's reaming post-modification has the dispersibility of excellence With good interface compatibility, the nanocomposite foaming agent agglomeration after institute's carrying out washing treatment is substantially changed Kind.Therefore, in the present invention by CBA is introduced have ultra-large aperture and finely dispersed reaming, In modified mesoporous silicon oxide, and alleviate nanocomposite foaming agent group in dry run by carrying out washing treatment Poly-so that the nanocomposite foaming agent not only particle size that the present invention provides is little, and to CBA Loading is high, it is thus possible to obtain the more preferable microcellular foam of foaming quality.
Accompanying drawing explanation
Fig. 1 is reaming mesoporous silicon oxide (EMS4) described in the embodiment of the present invention 1.1 and embodiment 1.2 Described in each modified mesoporous silicon oxide (KH550-EMS4, KH560-EMS4 and KH570-EMS4) Infrared spectrogram.
Fig. 2 is reaming mesoporous silicon oxide (EMS4) described in the embodiment of the present invention 1.1 and embodiment 1.2 Described in each modified 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 described in the embodiment of the present invention 1.1 mesoporous two Modified mesoporous silicon oxide described in silicon oxide (EMS4, amplification is 5000), embodiment 1.2 (KH550-EMS4, amplification is 5000 times, KH560-EMS4, amplification be 5000 times and KH570-EMS4, amplification is 5000 times) scanning electron microscope (SEM) figure.
Fig. 4-a and Fig. 4-b is respectively KH550-EMS4 and nanocomposite foaming agent OBSH-KH550-EMS4 solid-state nuclear magnetic resonance cross-pole SiClx spectrum (29Si CP/MAS NMR) spectrogram.
Fig. 5 is the solid state nmr of KH550-EMS4 and nanocomposite foaming agent OBSH-KH550-EMS4 Resonance cross polarization carbon spectrum (13C CP/MAS NMR) spectrogram.
Fig. 6-a is nanocomposite foaming agent gained sample after carrying out washing treatment described in the embodiment of the present invention 1.3 Scanning electron microscope (SEM) figure of the granular size pattern of F2.
Fig. 6-b is nanocomposite foaming agent gained sample after carrying out washing treatment described in the embodiment of the present invention 1.3 Scanning electron microscope (SEM) figure of the granular size pattern of F3.
Fig. 6-c is nanocomposite foaming agent gained sample after carrying out washing treatment described in the embodiment of the present invention 1.3 Scanning electron microscope (SEM) figure of the granular size pattern of F1.
Detailed description of the invention
The problem still having much room for improvement in view of the combined efficiency of current composite foamable agent, the present invention provides a kind of to be situated between Hole silicon dioxide is main body, the nanocomposite foaming agent with organic foaming agent as object.
One preferred embodiment in, the preparation process of nanocomposite foaming agent of the present invention is as follows:
Obtaining mesoporous silicon oxide by sol-gal process reaction, material of main part preparation is as follows: cetylamine is molten In isopropanol water solution (volume ratio 10:9), the ammonia regulation solution acid alkalinity adding 28% is 7.5-11.5, Being eventually adding tetraethyl orthosilicate, react 12-24h under uniform temperature, dehydrated alcohol rinses, centrifugal, calcining. Reaction temperature can be 20-45 DEG C, preferably 30 DEG C.
Described reaming mesoporous silicon oxide is by above-mentioned mesoporous silicon oxide and alkali metal salt soln infusion process And obtain, preparation process is as follows: above-mentioned mesoporous silicon oxide is dissolved in the alkali metal salt of 23% or the water-soluble of double salt In liquid, stir, stand dipping 3h, be placed in 110 DEG C of baking ovens and after 4h, put into Muffle furnace calcining.Its In, preferably lithium chloride, potassium nitrate or sodium chloride, lithium chloride and potassium nitrate double salt all can play reaming effect, Aperture adjustment scope is 11.0nm-35.8nm.More preferably sodium chloride, lithium chloride and the double salt of potassium nitrate, Reaming back aperture is 35.8nm.
Described reaming, modified mesoporous silicon oxide are obtained by above-mentioned reaming silicon dioxide chemical modification, real Material of main part preparation mentioned in example is as follows: at a certain temperature, by mesoporous two after above-mentioned double salt reaming Silicon oxide is dissolved in ethanol water, ultrasonic, and adding a certain amount of formula is YRnSiX3(wherein n=1 or >= 3) silane coupler, stirs 24h, sucking filtration, is dried.Wherein, modified for 1g mesoporous silicon oxide Silane coupler consumption can be 1-6mL, preferably 4mL；Reaction temperature can be 25-60 DEG C, excellent Elect 25 DEG C as.
Formula is YRnSiX3The silane coupler of (wherein n=1 or >=3), wherein Y is organic compound official Can roll into a ball, including-NH2、-HNCONH2、-HNCH2CH2NH2、-N3、 Deng, it is preferably-NH2,-HNCONH2,-HNCH2CH2NH2,-N3, more preferably-NH2、 -HNCONH2, most preferably-NH2；X is hydrolysis functional group, including-OCH3、-OCH2CH3、 OCH2CH2OCH3,-Cl etc., be preferably-OCH3、-OCH2CH3。
Described nanocomposite foaming agent is soaked with CBA by above-mentioned reaming, modified mesoporous silicon oxide Stain forms, and material of main part preparation mentioned in example is as follows: under conditions of organic solvent exists, generalization Learn foaming agent to be dissolved in organic solvent, be stirring evenly and then adding into above-mentioned reaming, modified mesoporous silicon oxide, super Sound 10min, normal temperature dipping 24h, gained sample alcohol or alcohol mixing wash liquid, be dried, and prepares mesoporous The embedded nanocomposite foaming agent of silicon-dioxide-substrate.Wherein, cleaning solvent includes but not limited to methanol or comprises The mixing washing liquid of methanol.
Present invention also offers above-mentioned nanocomposite foaming agent and prepare the application of microcellular foam, institute in example The material of main part preparation mentioned is as follows:
Under uniform temperature, a certain amount of above-mentioned nanocomposite foaming agent is joined in 10g epoxy resin, stirs Mix uniformly, add a certain amount of firming agent diethylenetriamine, quickly after stirring, move into the baking oven relaying of 80 DEG C Continuous solidification 24h.Wherein, reaction temperature can be 80 DEG C-100 DEG C, preferably 80 DEG C；
Cleaning solvent includes but not limited to methanol or the mixing washing liquid comprising methanol, preferably organic solvent, change Learn foaming agent and the near saturated solution of methanol；The addition of nanocomposite foaming agent can be 0.1g-0.3g, excellent Elect 0.2g as；The addition of firming agent can be 0.5mL-0.7mL, preferably 0.6mL, thus obtains ring Epoxy resins microcellular foam.
Nanocomposite foaming agent of the present invention and preparation thereof is further illustrated below by specific embodiment Methods and applications.
In the following embodiments, agents useful for same and facility information are as follows:
The double benzsulfamide of 4,4 '-oxo: lark prestige science and technology group.
Nitrogen adsorption-desorption curve: instrument: specific surface area and lacunarity analysis instrument, producer: those Austria of Beijing Moral Electron Technology Co., Ltd, model: SSA-6000E.
Cell diameter and cell density assay method: utilize the Nano Measurer software SEM to sample Figure carries out diameter measurement and number statistics, calculates mean cell diameter, further according to formula ρc=(Nm2/A)3/2Calculate cell density, be wherein cell density (individual/cm3), n is the abscess number (individual) in statistics area, M is amplification, and A is statistics area (cm3)。
Nuclear magnetic resonance analyser: producer: Brooker company of Germany, model: Bruker AV300,13C MAS NMR Test condition: rotor speed 12kHz, relaxation delay time 10s, scanning times is 5000-7000 time, Using glycine as chemical shift standards reference material, the chemical shift of its carbonyl carbon is 176.03ppm.
Scanning electron microscope: producer: FEI Co. of the U.S., model: Quanta2050S, with conducting resinl sample After being bonded on sample stage, metal spraying processes, and observes the pattern of powder sample.
The preparation of embodiment one nanocomposite foaming agent
The reaming procedure of embodiment 1.1 mesoporous silicon oxide
At 30 DEG C, 6g cetylamine is dissolved in 600mL isopropanol and 540mL water, adds 8.4mL 28% Ammonia spirit, regulation pH is 11.2, drips by the tetraethyl orthosilicate (TEOS) of 34.8mL, 30 DEG C stand one day, rinse with dehydrated alcohol, programmed temperature method calcining preparation, obtain mesoporous silicon oxide MS；Described programmed temperature method is: temperature is risen to 250 DEG C from room temperature by (1), constant temperature 30min；(2) Temperature is increased to again 450 DEG C, constant temperature 50min；(3) temperature is warming up to again 600 DEG C, constant temperature 4h.
Preparation molar concentration is the NaCl solution of 5mol/L, the LiCl solution of 5mol/L, 5mol/L respectively KNO3Solution, and mass ratio is NaCl, LiCl, KNO of 4:1:13Complex salt solution, and multiple The mass fraction of saline solution is 23%.Above-mentioned for 2g mesoporous silicon oxide is added separately to 100ml above-mentioned four Plant in saline solution, stir, impregnate 3h, after 110 DEG C of drying 4h, put into Muffle furnace calcining.Calcining is adopted With programmed temperature method, temperature is set as: rise to 300 DEG C (heating rate is 10 DEG C/min) from room temperature, permanent Temperature 30min, this temperature range is to adsorb water and the combustion decomposition of organic impurities in nano-particle, continues It is warming up to 600 DEG C (heating rate is 10 DEG C/min), after constant temperature 180min, stops heating, natural cooling Rear taking-up.Deionized water wash, microfilter is added after mesoporous silicon oxide after roasting reaming is ground Sucking filtration, washing is until without Cl-(the AgNO of 0.lmol/mL3Solution detects), put in baking oven, 80 DEG C Dry, obtain reaming mesoporous silicon oxide, be denoted as EMS1, EMS2, EMS3, EMS4 respectively.
The modifying process of embodiment 1.2 reaming mesoporous silicon oxide
Mesoporous silicon oxide EMS4 2g embodiment 1.1 obtained joins 20ml water and 180ml ethanol In mixed solution, mechanical agitation to uniformly, ultrasonic 30min.Add 4mL silane coupler γ-aminopropyl Triethoxysilane (KH550), magnetic agitation 24h, microfilter sucking filtration, it is dried, obtains KH550 Modified mesoporous silicon oxide, is denoted as KH550-EMS4.
In like manner, above-mentioned silane coupler is changed to the γ-glycidyl ether oxygen propyl trimethyl silane of same volume (KH560) or γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), under the same terms Modified obtain KH560 and KH570 modification mesoporous silicon oxide, be denoted as respectively KH560-EMS4 and KH570-EMS4。
The preparation of embodiment 1.3 nanocomposite foaming agent
Weigh 2.69g CBA 4, the double benzsulfamide (OBSH) of 4 '-oxo, be dissolved in 15Ml N, N '- In dimethylformamide (DMF), magnetic agitation is to uniformly.Weigh 0.5g embodiment 1.2 preparation KH550-EMS4 adds in above-mentioned solution, stirs, ultrasonic 10min, impregnates 24h under room temperature, micro- Hole filter sucking filtration.Washing liquid (2g 4,4 '-OBSH, 10mL N, N ' two is mixed with 10mL Methylformamide and 10mL methanol) washing after again with 10mL methanol wash, in 60 DEG C of baking ovens be dried 24h, Obtain nanocomposite foaming agent OBSH-KH550-EMS4, be denoted as F1.In the present embodiment, F1 with What OBSH-KH550-EMS4 referred to is nanocomposite foaming agent of the same race.
In like manner, it is changed to the mode of washing in said method not wash or 10mL methanol washing replacement 10mL Mixing washing liquid (2g 4,4 '-OBSH, 10mL N, N ' dimethylformamide and 10mL methanol) Wash with 10mL methanol again after washing, will after washing the nanocomposite foaming agent that obtain be denoted as respectively F2 and It is denoted as F3.
Embodiment 1.4 foaming product
The present embodiment is used for illustrating that nanocomposite foaming agent of the present invention is in preparing microcellular foam Application.At a certain temperature, adding of a certain amount of nanocomposite foaming agent after different mode of washing being processed Enter in 10g epoxy resin, carry out normal pressure foaming experiment adding a certain amount of firming agent diethylenetriamine. Mode of washing (A), nanocomposite foaming agent addition (B), blowing temperature (C) and firming agent are added Enter amount (D) and as level, carry out L9 (34) as 4 factors, 3 different states of each factor Orthogonal design, orthonormal design of experiments is shown in Table 2.Wherein A1 is convection drying, and A2 is to be dried after methanol washs, A3 be above-mentioned mixing washing liquid (2g 4,4 '-OBSH, 10mL N, N ' dimethylformamide and 10mL methanol) washing after again with 10mL methanol washing be dried；B1 is 0.1 gram, and B2 is 0.2 gram, B3 is 0.3 gram；C1 is 80 DEG C, and C2 is 90 DEG C, and C3 is 100 DEG C；D1 is 0.5mL, and D2 is 0.6mL, D3 is 0.7mL.
Table 1
Additionally, the present inventor adds following experiment of single factor:
Experiment 10:A2B2C1D3
Experiment 11:A1B2C1D3
Experiment 12: similar with testing 8 conditions, differs only in and the component mixing washing liquid is changed into: 2g 4,4 '- The double benzsulfamide of oxo, 20ml methanol and 20ml N, N ' dimethylformamide.
Experiment 13: similar with testing 8 conditions, differs only in and the component mixing washing liquid is changed into: 2g 4,4 '- The double benzsulfamide of oxo, 30ml methanol and 30ml N, N ' dimethylformamide.
The sample of embodiment 1.1-1.4 is carried out following sign:
1. pore structure
Detect MS respectively, the average pore size of EMS1, EMS2, EMS3 and EMS4, pore volume and Bi Biao Area.Wherein nitrogen adsorption-desorption curve is to use Beijing Bi Aode Electron Technology Co., Ltd to produce The full-automatic specific surface area of SSA-6000E type and lacunarity analysis instrument are measured from, according to Barrett-Joyner- Halenda (BJH) formula, calculates average pore size and pore volume by the desorption branch in adsorption isotherm, than Surface area is calculated according to Brunauer-Emmett-Teller (BET) formula, result such as table 2 below Shown in.
Table 2
Sample ID Average pore size (nm) Pore volume (cm3 g-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 is relatively big due to micropore proportion, and therefore its specific surface area is relatively big, Comparatively speaking, the EMS4 average pore size obtained after complex salt dipping is up to 35.8nm, and reaming effect is relative More preferably.
2. infrared detection
Respectively to EMS4, embodiment 1.2 preparation material (KH550-EMS4, KH560-EMS4 and KH570-EMS4) carrying out infrared spectrum analysis, the FTIR spectrum of each of which is as shown in Figure 1.
It will be seen from figure 1 that the characteristic absorption peak (1093cm of Si-O-Si key-1) the most substantially open up through modification Width, this is the characteristic absorption peak (1167cm of Si-O-C of modified generation-1, 1107cm-1And 1075cm-1) Superpose with the characteristic absorption peak of Si-O-Si key and to cause.And KH550 is modified at 1560cm-1Place goes out Having showed the bending vibration characteristic absorption peak of N-H in KH550, KH560 is modified at 2944cm-1Place occurs The characteristic absorption peak of methylene, KH570 is modified at 1719cm-1Place occurs in that the characteristic absorption of C=O Peak.Thus illustrating, mesoporous silicon oxide is modified by KH550, KH560 and KH570 success.
3. nuclear magnetic resonance, NMR
Respectively to EMS4, embodiment 1.2 preparation material (KH550-EMS4, KH560-EMS4 and KH570-EMS4) carry out solid-state nuclear magnetic resonance cross-pole SiClx spectrum (29Si CP/MAS NMR) analyze, Each of which29Si CP/MAS NMR spectra is as shown in Figure 2.
Figure it is seen that EMS4 only exists Q construction unit, modified, all generate silicon atom with The S construction unit that organic group is connected.Thus illustrating, mesoporous silicon oxide is by KH550, KH560 And KH570 success is modified.
4. scanning electron microscope analysis
Respectively to EMS4, embodiment 1.2 preparation material (KH550-EMS4, KH560-EMS4 and KH570-EMS4) being scanned ultramicroscope (SEM) to analyze, the SEM of each of which schemes such as Fig. 3-a To shown in Fig. 3-d.
From figure 3, it can be seen that EMS4 average diameter is about 800nm, but there is many more than 5 μm Aggregate.KH550-EMS4 granule shows a monodisperse distribution substantially, and KH560-EMS4 only exists very small amount Aggregate about 2 μm, there are 2 a small amount of μm to the aggregate of 4 μm in KH570-EMS4.Thus say Bright, modification reduces reunion, improves dispersion.
Wherein, the particle diameter of EMS4 and modified mesoporous silicon oxide is up to 0.4-1.2 μm.
5. nuclear magnetic resonance, NMR
To embodiment 1.3 preparation foaming agent F1 carry out solid-state nuclear magnetic resonance cross-pole SiClx spectrum (29Si CP/MAS NMR) analyze, KH550-EMS4's and F1 (i.e. OBSH-KH550-EMS4)29Si CP/MAS NMR spectra is as shown in Fig. 4-a to Fig. 4-b.
From Fig. 4-a and Fig. 4-b it can be seen that compared with KH550-EMS4, the S construction unit of F1 contains Amount reduces, and Q structural unit content increases.Thus illustrating, CBA has been enter into KH550-EMS4 Duct in, the polarization of Q construction unit is strengthened by CBA.
6. nuclear magnetic resonance, NMR
To embodiment 1.3 preparation foaming agent F1 carry out solid-state nuclear magnetic resonance cross polarization carbon spectrum (13C CP/MAS NMR) analyze, KH550-EMS4's and F1 (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's13On C CP/MAS NMR spectra Occur in that the characteristic absorption peak (100-170ppm) of obvious CBA (OBSH), and in document Pure OBSH's13C CP/MAS NMR spectra is compared, and phenyl ring limitation of movement in OBSH, at phenyl ring Spectral peak broadens.Thus illustrating, CBA the most successfully supports in the duct of KH550-EMS4.
7. scanning electron microscope analysis
Foaming agent F1-F3 to embodiment 1.3 preparation is scanned ultramicroscope (SEM) analysis respectively, The SEM of F2, F3 and F1 schemes respectively as shown in Fig. 6-a, Fig. 6-b and Fig. 6-c, figure detection understand F1 Particle diameter is 0.4-6.5 μm, and F3 particle diameter is 0.4-1 μm.
From Fig. 6-a to Fig. 6-c it can be seen that nanocomposite foaming agent is dispersed with by different mode of washing The biggest impact.The solvent DMF polarity used during preparing nanocomposite foaming agent is relatively big, adopts The dispersion contributing to nanocomposite foaming agent, employingization it is dried again after removing DMF with the solvent that polarity is less Learn the near saturated solution washing of foaming agent, while removing DMF, also can slow down CBA between hole Precipitation, it helps nanocomposite foaming agent preferably disperses.
8. scanning electron microscope analysis
Expanded material to embodiment 1.4 preparation is scanned ultramicroscope (SEM) analysis respectively, utilizes Above-mentioned SEM figure is carried out statistical analysis by Nano Measure software, and result is as shown in table 3 below.From table 3 Normal pressure foaming is carried out it can be seen that added in epoxy resin by the nanocomposite foaming agent of preparation, optimized Foaming condition is A3B2C1D3, and the epoxy foam mean cell diameter of preparation is 34.4 μm, Cell density is 1.3 × 106Individual/cm3。
Table 3
Embodiment two
Embodiment two is similar to the preparation process of embodiment one, differs only in: (1) is at nano combined In the preparation process of infusion, the quality of OBSH changes 1.5g into；Washing process is: mix washing liquid with 10mL After (2g 4,4 '-OBSH, 10mL N, N ' dimethylformamide and 10mL methanol) washing Wash with 10mL methanol again, 60 DEG C of baking ovens are dried 24h, obtain nanocomposite foaming agent.
Test after epoxy resin is foamed by 8 identical foaming methods can obtain with embodiment one, aperture ＜ The abscess percentage ratio of 50 μm is 80.3%, and mean cell diameter is 38.9 μm, and cell density is 9.7 × 105 Individual/cm3。
Embodiment three
Embodiment three is similar to the preparation process of embodiment one, differs only in: by nanocomposite foaming agent In preparation process, the quality of OBSH changes 3.5g into；Washing process is: with 10mL mix washing liquid (2g 4,4 '- OBSH, 10mL N, N ' dimethylformamide and 10mL methanol) washing after use 10mL again Methanol washs, and is dried 24h, obtains nanocomposite foaming agent in 60 DEG C of baking ovens.
Test after epoxy resin is foamed by 8 identical foaming methods can obtain with embodiment one, aperture ＜ The abscess percentage ratio of 50 μm is 72.6%, and mean cell diameter is 42.7 μm, and cell density is 7.8 × 105 Individual/cm3。
Embodiment four
Embodiment four is similar to the preparation process of embodiment one, differs only in: double salt used is that mass ratio is NaCl, LiCl, KNO of 4:1:13Complex salt solution, and the mass fraction of complex salt solution is 5%.
Washing process is: mix washing liquid (2g 4,4 '-OBSH, 10mL N, N ' with 10mL Dimethylformamide and 10mL methanol) washing after again with 10mL methanol wash, in 60 DEG C of baking ovens be dried 24h, obtains nanocomposite foaming agent.
Test after epoxy resin is foamed by 8 identical foaming methods can obtain with embodiment one, aperture ＜ The abscess percentage ratio of 50 μm is 76.2%, and mean cell diameter is 36.5 μm, and cell density is 6.7 × 105 Individual/cm3。
Embodiment five
Embodiment five is similar to the preparation process of embodiment one, differs only in: double salt used is that mass ratio is NaCl, LiCl, KNO of 4:1:13Complex salt solution, and the mass fraction of complex salt solution is 70%.
Washing process is: mix washing liquid (2g 4,4 '-OBSH, 10mL N, N ' with 10mL Dimethylformamide and 10mL methanol) washing after again with 10mL methanol wash, in 60 DEG C of baking ovens be dried 24h, obtains nanocomposite foaming agent.
Test after epoxy resin is foamed by 8 identical foaming methods can obtain with embodiment one, aperture ＜ The abscess percentage ratio of 50 μm is 67.4%, and mean cell diameter is 47.1 μm, and cell density is 7.2 × 105 Individual/cm3。
Comparative example one
Comparative example one is similar to the preparation process of embodiment one, differs only in: embodiment 1.2 reaming be situated between EMS4 used in the modifying process of hole silicon dioxide changes not doing the mesoporous silicon oxide of expanding treatment into MS。
Test after epoxy resin is foamed by 8 identical foaming methods can obtain with embodiment one, aperture ＜ The abscess percentage ratio of 50 μm is 77.8%, and mean cell diameter is 39.5 μm, and cell density is 3.3 × 105 Individual/cm3。
Comparative example two
Comparative example two is similar to the preparation process of embodiment one, differs only in: double salt used is that mass ratio is NaCl, LiCl, KNO of 4:1:13Complex salt solution, and the mass fraction of complex salt solution is 80%.
Washing process is: mix washing liquid (2g 4,4 '-OBSH, 10mL N, N ' with 10mL Dimethylformamide and 10mL methanol) washing after again with 10mL methanol wash, in 60 DEG C of baking ovens be dried 24h, obtains nanocomposite foaming agent.
Test after epoxy resin is foamed by 8 identical foaming methods can obtain with embodiment one, aperture ＜ The abscess percentage ratio of 50 μm is 50.6%, and mean cell diameter is 53.2 μm, and cell density is 4.5 × 105 Individual/cm3。
In sum, preparation method of the present invention successfully CBA introducing had large aperture and divide Dissipating in uniform modified mesoporous silicon oxide, the nanocomposite foaming agent not only particle size prepared is little and right The loading of CBA is high, and the microcellular foam cell density prepared is big, functional, has wide General application prospect.

Claims (20)

1. a nanocomposite foaming agent, it is characterised in that by modified mesoporous silicon oxide and 4,4 '-oxo Double benzsulfamides are composited, described modified mesoporous silicon oxide and 4, the quality of the double benzsulfamide of 4 '-oxo Ratio is 1:(3-7)；Wherein, described modified mesoporous silicon oxide is to be sequentially passed through expansion by mesoporous silicon oxide Obtain behind hole and graft modification.
Nanocomposite foaming agent the most according to claim 1, wherein, described modified meso-porous titanium dioxide The mass ratio of silicon and the double benzsulfamide of 4,4 '-oxo is 1:(4-6).
Nanocomposite foaming agent the most according to claim 1 and 2, wherein, described nano combined The particle diameter of infusion is 0.8-10 μm, preferably 0.4-6.5 μm, more preferably 0.4-1 μm.
4. according to the nanocomposite foaming agent described in any one of claim 1-3, wherein, described mesoporous dioxy The aperture of SiClx is 2-40nm, preferably 10-36nm.
5. the preparation method of nanocomposite foaming agent described in any one of claim 1-4, it is characterised in that: will After mesoporous silicon oxide sequentially passes through reaming and graft modification, obtain modified mesoporous silicon oxide；Modification is situated between Hole silicon dioxide and 4, the double benzsulfamide of 4 '-oxo is compound obtains nanocomposite foaming agent, wherein, described in change Property mesoporous silicon oxide and the mass ratio of the double benzsulfamide of 4,4 '-oxo be 1:(3-7).
Preparation method the most according to claim 5, wherein, the preparation of described nanocomposite foaming agent Method comprises the steps:
(1) with salt impregnation method, mesoporous silicon oxide is carried out expanding treatment；
(2) by the mesoporous silicon oxide addition modifying agent after reaming is modified, modified mesoporous two are obtained Silicon oxide；
(3) above-mentioned changing will be added containing the N of the double benzsulfamide of 4,4 '-oxo, N '-dimethyl formamide solution Property mesoporous silicon oxide in, sequentially pass through ultrasonic, washing after, obtain nanocomposite foaming agent.
Preparation method the most according to claim 6, wherein, described in step (1) in salt impregnation method The salt used includes the mixture of one or more alkali metal salts；The mass concentration of described salt is 5-70%, preferably 20-30%.
Preparation method the most according to claim 7, wherein, described alkali metal salt is sodium chloride, chlorine Change the double salt of one or more compositions of lithium or potassium nitrate.
9. according to the preparation method described in any one of claim 6-8, wherein, expand described in step (1) The process that hole processes comprises the steps:
After mesoporous silicon oxide is added saline solution, calcine with programmed temperature method, described temperature programming Journey comprises the steps:
(1) temperature is risen to the first calcining heat, constant temperature 30-60min from room temperature；
(2) temperature is warming up to the second calcining heat, constant temperature 3-5h from the first calcining heat；
Wherein, described first calcining heat is 200-300 DEG C, and the second calcining heat is 400-700 DEG C.
Preparation method the most according to claim 9, wherein said mesoporous silicon oxide and saline solution Ratio is 1g:(0.1-100) ml.
11. according to the preparation method described in any one of claim 6-10, wherein, described mesoporous silicon oxide Preparation process comprise the steps:
Being added by tetraethyl orthosilicate in the organic solvent containing cetylamine, calcining obtains mesoporous silicon oxide；Institute The ratio stating tetraethyl orthosilicate and cetylamine is (30-40) ml:(5-7) g.
12. according to the preparation method described in any one of claim 6-11, and wherein, described modifying agent is silane Coupling agent, preferably gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethyl silane or γ- (methacryloxypropyl) propyl trimethoxy silicane.
13. according to the preparation method described in any one of claim 6-12, wherein, described in step (3) Containing the N of the double benzsulfamide of 4,4 '-oxo, in N '-dimethyl formamide solution, 4, the double benzsulfamide of 4 '-oxo Concentration be 0.2mo/L～0.5mol/L, preferably 0.4-0.5mol/L.
14. according to the preparation method described in any one of claim 6-13, wherein, described washing process includes Following step:
(1) wash by mixing washing liquid；
(2) again with methanol is washed；
Wherein, described mixing washing liquid include methanol, 4, the double benzsulfamide of 4 '-oxo and N, N '-dimethyl formyl Amine.
15. preparation methoies according to claim 14, wherein, in described mixing washing liquid, with every gram 4, the double benzenesulfonamide of 4 '-oxo, including methanol and the N of 5-15ml of 5-15ml, N '-dimethyl Methanamide, It is preferably methanol and the N of 5-10ml, the N '-dimethyl Methanamide of 5-10ml.
16. 1 kinds of nanocomposite foaming agents, it is characterised in that by making described in any one of claim 6-15 Preparation Method prepares.
17. 1 kinds of foaming products, it is characterised in that include nanocomposite foaming agent, firming agent and asphalt mixtures modified by epoxy resin Fat, described nanocomposite foaming agent is multiple selected from nanometer described in claim 1-5 or any one of claim 16 Close foaming agent.
18. according to foaming product described in claim 17, wherein, and described nanocomposite foaming agent, firming agent It is: (1-5): (4-10): 100 to be preferably (1-3): (4-10) with the weight ratio of epoxy resin: 100。
19. 1 kinds of epoxy resin microcellular foams, it is characterised in that described in claim 17 or 18 Obtain after foaming product mixing, solidification.
Nanocomposite foaming agent described in 20. claim 1-5 or any one of claim 16, or right will Ask foaming product described in 17 or 18 in the application in foaming agent field.
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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
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