CN106478053A - A kind of mesoporous composite material and preparation method thereof and the purposes in thermostable heat-isolating material is prepared - Google Patents

A kind of mesoporous composite material and preparation method thereof and the purposes in thermostable heat-isolating material is prepared Download PDF

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Publication number
CN106478053A
CN106478053A CN201610844206.1A CN201610844206A CN106478053A CN 106478053 A CN106478053 A CN 106478053A CN 201610844206 A CN201610844206 A CN 201610844206A CN 106478053 A CN106478053 A CN 106478053A
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mesoporous
silicon
composite
fiber
mesoporous material
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栾玉成
徐海泉
张琼琼
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SUZHOU WANNA NEW MATERIAL TECHNOLOGY CO., LTD.
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Shanghai New Mstar Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
    • C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The present invention relates to Material Field, more particularly to a kind of mesoporous composite material and preparation method thereof and the purposes in thermostable heat-isolating material is prepared.The present invention provides a kind of mesoporous composite material, and including mesoporous material and fiber, the mesoporous material is silicon-based mesoporous material, and the fiber is the fiber containing silicon, compound with Si O Si key between the mesoporous material and fiber.The present invention is by mesoporous material and fiber composite by way of heat treatment, and further composite is studied, so as to provide a kind of composite mesoporous heat-insulating heat-preserving material compound with Si O Si key at high temperature with good heat-resistant stability and low thermal conductivity, the composite construction of the composite keeps stable at high temperature, with good industrialization prospect.

Description

A kind of mesoporous composite material and preparation method thereof and preparing thermostable heat-isolating material Purposes in material
Technical field
The present invention relates to Material Field, more particularly to a kind of mesoporous composite material and preparation method thereof and resistance to height is being prepared Purposes in warm heat-insulating heat-preserving material.
Background technology
Heat-insulating heat-preserving material can be widely applied to various fields, the huge number of traditional heat-insulating heat-preserving material, for example Foam glass, calcium silicates, expanded pearlite cotton, fiberglass products, polyurethane and expandable polystyrene plate etc., but these materials Thermal conductivity factor typically all higher, also there are problems of for high molecular foam material inflammable, for a lot For use occasion, such heat insulation and preservation effect is not still ideal.Now, global heat preserving and insulating material is just towards height Effect, energy-saving and environmental protection integration direction are developed, and while Development of Novel heat preserving and insulating material, more emphasize targetedly to improve Insulating efficiency and reduces cost in recent years, start someone aeroge and fiber are carried out compound a kind of new heat-insulated with offer Insulation material, but these insulation materials yet suffer from various problems, and such as resistance to elevated temperatures is not good, be combined unstable, high cost Deng.So the performance improvement to such material remains the study hotspot of this area one.
Content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of mesoporous composite material and its system Preparation Method and purposes, for solving the problems of the prior art.
For achieving the above object and other related purposes, first aspect present invention provides a kind of mesoporous composite material, including Mesoporous material and fiber, the mesoporous material are silicon-based mesoporous material, and the fiber is the fiber containing silicon, the mesoporous material Compound with-Si-O-Si- key and fiber between；
The aperture of mesoporous composite material intermediary Porous materials is 2-50nm；
The pore volume of mesoporous composite material intermediary Porous materials is 0.1-2.5ml/g；
The hole wall of mesoporous composite material intermediary Porous materials is 1-10nm；
The porosity of mesoporous composite material intermediary Porous materials is 20-89%.
In some embodiments of the present invention, the varying aperture scope of the mesoporous material is not more than 30nm, and/or described The excursion of mesoporous material hole wall is not more than 5nm.
In some embodiments of the present invention, the varying aperture scope of the mesoporous material is not more than 20nm, and/or described The excursion of mesoporous material hole wall is not more than 3nm.
In some embodiments of the present invention, the silicon-based mesoporous material is selected from M41S series silicon-based mesoporous material, HMS system Row silicon-based mesoporous material, MSU series silicon-based mesoporous material, SBA series silicon-based mesoporous material, FDU series silicon-based mesoporous material, ZSM series silicon-based mesoporous material, KIT series silicon-based mesoporous material, HOM series silicon-based mesoporous material, the silicon-based mesoporous material of FSM series Material, AMS series silicon-based mesoporous material, IBN series silicon-based mesoporous material, TUD series silicon-based mesoporous material in one kind or they Any combination.
In some embodiments of the present invention, the silicon-based mesoporous material is for pure silicon based mesoporous material or doped with except Si, O The silicon-based mesoporous material of other elements in addition.
In some embodiments of the present invention, the element of doping selected from C, B, Ti, V, Cr, Co, Mn, Fe, Ni, Zr, Cu, A kind of or their any combination in Ca, Cd, Sn, Ce, Sm, Pr, Nb, W, La, Al, In, Ga, Ge, Ru, Zn, Mo.
In some embodiments of the present invention, doping by mass percentage, is silicon-based mesoporous material gross mass 0.001%-40%.
In some embodiments of the present invention, doping by mass percentage, is silicon-based mesoporous material gross mass 0.1%-20%.
In some embodiments of the present invention, doping by mass percentage, is the 2- of silicon-based mesoporous material gross mass 15%.
In some embodiments of the present invention, the fiber is the silane modified rear fiber for obtaining.
In some embodiments of the present invention, a kind of in the mineral fibres and inorfil of the fiber or they Any combination.
In some embodiments of the present invention, the mesoporous material is 1 with the mass ratio of fiber：0.01-50.
Second aspect present invention provides the preparation method of described mesoporous composite material, comprises the steps：By mesoporous material Material precursor is mixed with fiber and/or fibre, is heat-treated, and prepares the mesoporous composite material.
In some embodiments of the present invention, the temperature of the heat treatment is 25-1000 DEG C；
In some embodiments of the present invention, the mass ratio of the mesoporous material presoma and fiber and/or fibre For 1：0.01-50.
In some embodiments of the present invention, the preparation method of the mesoporous material presoma comprises the steps：By silicon Source prepares mesoporous material presoma under conditions of structure directing agent, solvent are present.
In some embodiments of the present invention, the silicon source is organic silicon source and/or inorganic silicon source.
In some embodiments of the present invention, the structure directing agent is surfactant type structure directing agent or non-surface Active agent formulation structure directing agent.
In some embodiments of the present invention, the silicon source is 1 with the mol ratio of structure directing agent：0.0001-3.
In some embodiments of the present invention, the silicon source is 1 with the mol ratio of solvent：2-300.
In some embodiments of the present invention, by silicon source under conditions of the presence of structure directing agent, solvent and catalyst, system Standby acquisition mesoporous material presoma, reaction system are acid, neutral or alkaline, and the pH of reaction system is 0.5-12.
In some embodiments of the present invention, the catalyst selected from acid catalyst, the one kind in base catalyst or they Any combination.
Third aspect present invention provides purposes of the mesoporous composite material in heat-insulating heat-preserving material is prepared.
Specific embodiment
Embodiments of the present invention are described below by way of specific instantiation, those skilled in the art can be by this specification Disclosed content understands other advantages of the present invention and effect easily.
The present invention by mesoporous material and fiber composite by way of heat treatment, so as to provide one kind with-Si-O-Si- The compound high temperature resistant composite mesoporous heat-insulating heat-preserving material of key, so as to there is provided a kind of with the composite mesoporous of good heat-proof quality While material so that mesoporous composite material has stable internal structure.
In this application, " mesoporous material " is often referred to porous material of the aperture between 2-50nm.
In this application, " ordered mesoporous material " is often referred to aperture between 2～50nm, the homogeneous and regular duct in aperture The mesoporous material of structure, the regular pore canal structure are often referred to the pore passage structure being repeated cyclically.
In this application, the main component that " silicon-based mesoporous material " is often referred to composition skeleton is the mesoporous material of silica Material.
In this application, " fiber " is often referred to the material being made up of continuous or discrete filament.
In this application, " fibre " is often referred to the product that at least a portion using fiber as raw material is prepared.
In this application, "-Si-O-Si- key " is often referred to two silicon atoms and forms Si-O key with oxygen atom respectively, forms two Between individual silicon atom, there is the structure of oxygen atom at interval.
In this application, " silicon source " is often referred to participate in reaction in mesoporous material preparation process, and provides silicon unit in product The material of element.
In this application, " catalyst " is often referred in chemical reaction to change reactant chemical reaction rate and not change Chemical balance, and the material that the quality of itself and chemical property are not all changed before and after chemical reaction.
In this application, " presoma " is often referred to prepare the material of target product through series of steps.
In this application, " structure directing agent " be often referred in the preparation process of mesoporous material can be to its product structure tool There is the material of guide effect.
In this application, " heat preserving and insulating material " is often referred to the material to hot-fluid with notable resistance.
Mesoporous composite material
One aspect of the present invention provides a kind of mesoporous composite material, and including mesoporous material and fiber, the mesoporous material is silicon Based mesoporous material, the fiber are the fiber containing silicon, compound with-Si-O-Si- key between the mesoporous material and fiber.
In mesoporous composite material provided by the present invention, mesoporous material can be silicon-based mesoporous material, and fiber can be contained There is the fiber of silicon, in the preparation, Si-OH functional group can be formed in mesoporous material presoma and fiber, and permissible further Make Si-OH functional group that polycondensation (for example, it is possible to by way of heat treatment) to occur, so that the Si in mesoporous material (for example, is constituted and be situated between Si in Porous materials silica skeleton) and fiber in Si between compound with-Si-O-Si- key.
Further, the present inventor is had found through a large amount of explorative experiment, and some mesoporous composite materials have good at high temperature Good heat-resistant stability and low thermal conductivity, the high temperature can be for example be not less than 450 DEG C, 700 DEG C, 1000 DEG C, 1300 DEG C, 1600 DEG C or 2000 DEG C of environment temperature；Described can specifically refer to mesoporous composite material in height with good heat-resistant stability After temperature lower a period of time (can be for example 0.5h, 1h, 2h, 3h, 4h, 6h, 8h, 12h, 16h, 24h, 2 days, 3 days, 4 days, 6 My god, 8 days, 10 days etc.) hardness and brittleness are nothing significant change, and/or do not occur obvious efflorescence, hole to cave in, and/or composite Shrinkage factor is not more than 5%, is not more than 4%, is not more than 3%, is not more than 2% or no more than 1%；The low thermal conductivity is permissible Refer to that the thermal conductivity factor of mesoporous composite material is not higher than 0.040w/ (m k), not higher than 0.035w/ (m k), not higher than 0.030w/ (m k), not higher than 0.025w/ (m k), not higher than 0.020w/ (m k), not higher than 0.015w/ (m k) are not higher than 0.010w/(m·k).The mesoporous composite material intermediary Porous materials with good heat-resistant stability and low thermal conductivity Aperture can be generally 2-50nm, 2-45nm, 2-40nm, 2-35nm, 2-32nm, 2-30nm, 2-28nm, 2-26nm, 2-24nm, 2-22nm、2-20nm、2-3nm、3-4nm、4-5nm、5-6nm、6-7nm、7-8nm、8-9nm、9-10nm、10-11nm、11- 12nm, 12-13nm, 13-14nm, 14-15nm, 15-16nm, 16-17nm, 17-18nm, 18-19nm or 19-20nm；The tool The pore volume for having the mesoporous composite material intermediary Porous materials of good heat-resistant stability and low thermal conductivity can be generally 0.1- 2.5ml/g、0.3-2ml/g、0.4-1.8ml/g、0.5-1.6ml/g、0.5-1.5ml/g、0.5-1.3ml/g、0.5-1.2ml/ g、1.0-1.5ml/g、1.5-2.0ml/g、2.0-2.5ml/g；Described with good heat-resistant stability and low thermal conductivity The hole wall of mesoporous composite material intermediary Porous materials can be generally 1-10nm, 1-9nm, 1-8nm, 1-7nm, 1-6nm, 1-5nm, 1- 4nm, 1-3nm, 1-2nm, 1.5-8nm, 2-6nm, 2-3nm, 3-4nm, 4-5nm, 5-6nm, 6-7nm, 7-8nm, 8-9nm or 9- 10nm.The mesoporous material of the mesoporous composite material intermediary Porous materials with good heat-resistant stability and low thermal conductivity Porosity can be 20-89%, 30-80%, 40-75%, 50-70%, 20-30%, 30-39%, 39-49%, 49-59%, 59-64%, 64-69%, 69-74%, 74-79%, 79-84% or 84-89%.
As a rule, the method for adjustment of aperture in mesoporous material preparation process, pore volume, hole wall size, porosity is for this Should be known for skilled person.For example, it is possible to reference to " Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300pores.Science,1998,279,548- 552 " method gone out given in, adjusts the aperture of the mesoporous composite material.Again for example, it is possible to reference to " Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 Pores.Science, 1998,279,548-552 " method gone out given in, adjusts the pore volume of the mesoporous composite material.Again For example, it is possible to reference to " Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300Pores.Science, 1998,279,548-552 " method gone out given in, adjusts and is given an account of The size of the hole wall of hole composite material.Again for example, it is possible to by adjusting the aperture of mesoporous material and/or the size of hole wall, adjust The porosity of the whole mesoporous composite material.
In mesoporous composite material provided by the present invention, the mesoporous material can be ordered into mesoporous material, or Unordered mesoporous material (for ordered mesoporous material).Usually aperture is homogeneous and/or hole wall is homogeneous for the mesoporous material Mesoporous material, the homogeneous excursion that may refer to aperture in the aperture be not more than 30nm, be not more than 28nm, be not more than 26nm, be not more than 24nm, be not more than 22nm, be not more than 20nm, be not more than 18nm, be not more than 16nm, be not more than 14nm, be not more than 12nm, be not more than 10nm, be not more than 8nm, be not more than 6nm, be not more than 4nm, be not more than 2nm, be not more than 1nm, be not more than 0.5nm or no more than 0.1nm；The homogeneous excursion that may refer to hole wall of the hole wall no more than 3nm, no more than 2.8nm, No more than 2.6nm, be not more than 2.4nm, be not more than 2.2nm, be not more than 2nm, be not more than 1.8nm, be not more than 1.6nm, be not more than 1.4nm, be not more than 1.2nm, be not more than 1.0nm, be not more than 0.8nm, be not more than 0.6nm, be not more than 0.4nm, be not more than 0.2nm or no more than 0.1nm.
In mesoporous composite material provided by the present invention, silicon-based mesoporous material can be that the silicon-based mesoporous material of pure silicon (is situated between Porous materials skeleton is all made up of silica), or the silicon-based mesoporous material doped with other elements in addition to Si, O.Silicon The example of based mesoporous material can include but is not limited to M41S series silicon-based mesoporous material, HMS series silicon-based mesoporous material, MSU Serial silicon-based mesoporous material, SBA series silicon-based mesoporous material, FDU series silicon-based mesoporous material, ZSM series silicon-based mesoporous material, KIT series silicon-based mesoporous material, HOM series silicon-based mesoporous material, FSM series silicon-based mesoporous material, the silicon-based mesoporous material of AMS series Material, IBN series silicon-based mesoporous material, TUD series silicon-based mesoporous material, other orderly or unordered silicon-based mesoporous materials etc..Described The element adulterated in silicon-based mesoporous material can be the various elements suitable for being doped to silicon-based mesoporous material, these yuan Element example include but is not limited to C, B, Ti, V, Cr, Co, Mn, Fe, Ni, Zr, Cu, Ca, Cd, Sn, Ce, Sm, Pr, Nb, W, La, A kind of or their any combination in Al, In, Ga, Ge, Ru, Zn or Mo etc..These elements generally instead of Jie after doping In Porous materials in silica skeleton Si element position, the doping method of these elements all should for a person skilled in the art It is known, for example, doping method is referred to " Postsynthesis, characterization and catalytic properties in alkene epoxidation of hydrothermally stable mesoporous Ti-SBA- 15, Chem.Mater., 2002,14：The method gone out given in 1657-1664 ", specific doping by mass percentage, can Be the 0.001-40% of silicon-based mesoporous material gross mass, 0.005-30%, 0.01%-40%, 0.05-35%, 0.1-30%, 0.2-25%, 0.3-20%, 0.4-15%, 0.5-12%, 0.6-10%, 0.7-9%, 0.8-8%, 0.8-1%, 1-2%, 2- 3%th, 3-4%, 4-5%, 5-6%, 6-7%, 7-8%, 8-9%, 9-10%, 10-11%, 11-12%, 12-13%, 13- 14% or 14-15%.
In mesoporous composite material provided by the present invention, the fiber can be the various fibers containing silicon, described contain The fiber of silicon can be itself i.e. the fiber containing element silicon, or some through modification after acquisition contain element silicon Fiber.It is known for a person skilled in the art fiber to be modified to obtain the method for the fiber containing element silicon , for example, be referred to " crosslinked with silicane of superhigh molecular weight polyethylene fibers is modified, synthetic fibers, and 2004,33 (4)：1-3”、 " several frequently seen inorfil Progress in Modification, textile technology are in progress, and 2015 (2)：11-13 ", " surface modifier is fine to plant The impact of dimension/PP composite material mechanical property, Beijing University of Chemical Technology's journal：Natural science edition, 2001,28 (3)：85-87” Given in the method that goes out.Fiber is modified with obtain the fiber containing element silicon during spendable material include but It is not limited to vinyl trichlorosilane, VTES, vinyltrimethoxy silane, three (2- methoxyl group of vinyl Ethyoxyl) silane, Silane coupling reagent KH-570, organosilane crosslinked polyethylene crosslinking agent, vinyl silane triisopropoxide, vinyl Three iso-propenyloxysilanes, methylvinyldichlorosilane, methyl vinyl diethoxysilane, MTES, The double trimethoxy silicon substrate ethane of methylvinyldimethoxysilane, 1,2-, phenyl trichlorosilane, phenyl triethoxysilane, Phenyltrimethoxysila,e, dimethoxydiphenylsilane, dichloromethyl phenylsilane, aminomethyl phenyl diethoxy silane, first Base phenyidimethoxysilane, vinyltriacetoxy silane, methyl triacetoxysilane, vinyl tributanoximo silicon A kind of in alkane, methyl tributanoximo silane, four butanone oximino silanes, tetraethyl orthosilicate, methyl silicate etc. or they Any combination.In the fiber containing silicon, the content of element silicon is not particularly limited, as long as the not goal of the invention to the present invention Produce restriction, for example, in terms of the gross mass of fiber, the content of element silicon can be total fiber mass 0.01-0.1%, 0.1-1%, 1-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, 35-40%, 40-45%, 45-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-75% or 75-80%；Again for example, after for modification The fiber containing element silicon for obtaining, in terms of the gross mass of fiber, in modified fibre, the content of silane can be 1-5%, 5- 10%th, 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, 35-40%, 40-45% or 45-50%.
In mesoporous composite material provided by the present invention, the fiber can be mineral fibres, and mineral fibres is often referred to fibre The fiber obtained in the Minerals And Rocks of dimension shape structure, for example, can be including but not limited to SiC fiber, SiN fiber, aluminium silicate fiber A kind of or their any combination in dimension, magnesium silicate fiber, ca silicate fibre etc..
In mesoporous composite material provided by the present invention, the fiber can also be chemical fibre, and the chemical fibre leads to Often refer to through the fiber for preparing of chemical treatment, for example, can be including but not limited in synthetic fibers and inorfil Plant or their any combination.The synthetic fibers are often referred to the material for itself not containing cellulose or protein as raw material system The standby fiber for obtaining, the synthetic fibers can for example include but is not limited to polyester fiber (terylene), Fypro (polyamide fibre Or nylon), vinal (polyvinyl), polyacrylonitrile fibre (acrylic fibers), polypropylene fibre (polypropylene fibre), polyvinyl chloride fibre A kind of or their any combination in (polyvinyl chloride fibre) etc..The inorfil is often referred to fine with natural inorganic thing or phasphorus-containing polymer The fiber prepared for raw material is tieed up, the example of the inorfil includes but is not limited to glass fibre, metallic fiber, carbon fibre Dimension, quartz fibre, boron fibre, ceramic fibre, mineral wool, high silica fiber, alumina fibre, rock wool, basalt fibre, Mo Lai A kind of or their any combination in mineral wool, phosphate fiber, alumina silicate fibre, refractory fibre.
Mesoporous composite material provided by the present invention can be the various forms of fiber or fibre in prior art, example Can be such as wire rod, powder etc., it is also possible to form fibrage further, for example, can be including but not limited to sheet material, coiled material etc., Can also be other various regular or irregular forms.
Those skilled in the art can determine mesoporous material according to the property of required mesoporous composite material, purposes and form And/or the parameter of fiber.For example, the mesoporous material can be 1 with the mass ratio of fiber:0.01-50、1:0.01-40、1: 0.01-30、1:0.01-20、1:0.1-50、1:0.1-40、1：0.1-30、1：0.1-20、1：0.1-10、1：0.1-0.2、1： 0.2-0.3、1：0.3-0.4、1：0.4-0.5、1：0.5-0.6、1：0.6-0.7、1：0.7-0.8、1：0.8-0.9、1：0.9-1、 1：1-2、1：2-3、1：3-4、1：4-5、1：5-6、1：6-7、1：7-8、1：8-9、1：9-10、1：10-12、1：12-14、1：14- 16、1：16-18、1：18-20、1：20-25、1：25-30、1:30-40 or 1:40-50.As a rule, those skilled in the art In the adjustable preparation process amount used by raw material (for example, silicon source, fiber), adjusts the mesoporous composite material intermediary hole material Material and the mass ratio of fiber.
The preparation method of mesoporous composite material
Another aspect of the present invention provides the preparation method of the mesoporous composite material.
The preparation method of mesoporous composite material provided by the present invention can include by mesoporous material presoma and fiber and/ Or fibre mixing, heat treatment, prepare the mesoporous composite material.
In preparation method provided by the present invention, the fiber can be the fiber containing silicon, in mesoporous material presoma Si-OH functional group and fiber in Si-OH functional group polycondensation can occur, can be formed mesoporous material silica skeleton knot Structure, can also make between Si in mesoporous material (for example, constituting the Si in mesoporous material silica skeleton) and the Si in fiber with- Si-O-Si- key is combined, and makes to form stable composite construction between fiber and/or fibre and mesoporous material.
In preparation method provided by the present invention, the heat treatment is often referred to the temperature control of reaction system in 25-50 ℃、50-100℃、100-150℃、150-200℃、200-250℃、250-300℃、300-350℃、350-400℃、400- 450℃、450-500℃、500-550℃、550-600℃、600-650℃、650-700℃、700-750℃、750-800℃、 800-850 DEG C, 850-900 DEG C, 900-950 DEG C or 950-1000 DEG C.Mode for heat treatment is not particularly limited, as long as The goal of the invention to the present invention does not produce restriction.Those skilled in the art can adjust reaction time, example according to reaction system Such as, heat treatment time, then for example, composite after heat treatment can be adjusted according to the mass ratio of mesoporous material presoma and fiber Outward appearance and weight can consider that reaction is completed when not changing, the reaction time, typically 0.2-8 hour, 0.4-7 were little When, 0.5-6 hour, 1-8 hour, 2-10 hour, 3-12 hour, 4-15 hour, 5-20 hour, 6-25 hour, 0.5-1 hour, 1-1.5 hour, 1.5-2 hour, 2-2.5 hour, 2.5-3 hour, 3-3.5 hour, 3.5-4 hour, 4-4.5 hour, 4.5-5 are little When, 5-5.5 hour, 5.5-6 hour, 6-7 hour, 7-8 hour, 8-9 hour, 9-10 hour, 10-11 hour, 11-12 hour, 12-13 hour, 13-14 hour, 14-15 hour, 15-18 hour, 18-20 hour, 20-22 hour or 22-25 hour.
In preparation method provided by the present invention, those skilled in the art can adjust mesoporous material forerunner according to target product Body and the ratio of fiber and/or fibre, for example, it is possible to according to mesoporous composite material intermediary Porous materials and the mass ratio of fiber Adjustment mesoporous material presoma and fiber and/or the usage amount of fibre, the method for these adjustment is for people in the art Should be all known for member, for example, the ratio of the mesoporous material presoma and fiber and/or fibre can be 1: 0.01-50、1:0.01-40、1:0.01-30、1:0.01-20、1:0.1-50、1:0.1-40、1：0.1-30、1：0.1-20、1： 0.1-4、1：0.1-8、1：0.1-12、1：0.1-16、1：0.15-7、1：0.19-6、1：0.22-5、1：0.25-4、1：0.5-6、 1：1-20、1：1-15、1：1-10、1：1-5、：0.25-0.5、1：0.5-0.75、1：0.75-1、1：1-1.5、1：1.5-2、1：2- 2.5、1：2.5-3、1：3-3.5、1：3.5-4、1：4-5、1：5-6、1：6-7、1：7-8、1：8-9、1：9-10、1：10-11、1： 11-12、1：12-15、1：15-17、1：17-20、1：20-30、1:30-40 or 1:40-50.
In preparation method provided by the present invention, mesoporous material presoma can be that silicon source is deposited in structure directing agent, solvent Under the conditions, can be more specifically under conditions of structure directing agent, solvent and catalyst are present, through hydrolysis, condensation, be aged The mesoporous material presoma that is undried and/or removing structure directing agent (mesoporous material under synthesis initial state) for being formed afterwards.
The preparation method of mesoporous composite material provided by the present invention can also be included silicon source in structure directing agent, solvent Under conditions of presence, can be more specifically structure directing agent, solvent and catalyst exist under conditions of, through hydrolysis, condensation, old Change and mesoporous material presoma is prepared, for example, can be mesoporous material precursor solution.Described prepare mesoporous material before During driving body, silicon source generally can occur hydrolysis with water, can be polymerized between the product of gained hydrolysis Reaction, the mechanism of hydrolysis are as follows：
Inorganic silicon source (SiCl4) there is hydrolysis：
nSiCl4+4nH2O→nSi(OH)4+4HCl
There is hydrolysis in inorganic silicon source (amorphous silica, silica gel, sodium metasilicate etc.)：
nSiO2+2nNaOH→nNa2SiO3+nH2O
nNa2SiO3+nH2O+2nHCl→nSi(OH)4+2nNaCl
There is hydrolysis in organic silicon source：
There is polymerisation between hydrolysate：
nSi(OH)4→nSiO2+2nH2O
In preparation method provided by the present invention, silicon source can be that this area is various suitable for preparing the organic of mesoporous material Silicon source and/or inorganic silicon source, the silicon source usually contain element silicon, and those skilled in the art can be according to the species of mesoporous material Determine the silicon source used in preparation process.For example, the inorganic silicon source can be including but not limited to silicon tetrachloride, silicic acid Sodium, amorphous silica, Ludox, diatomite, clay, rice hull ash, silica gel, Cab-O-Sil silica, gas phase titanium dioxide A kind of or their any combination in silicon etc..Again for example, organic silicon source can be including but not limited to as shown in Equation 1 Compound：
Wherein, R1, R2, R3, R4 independently can represent hydrogen atom, have side chain or unbranched, saturation or undersaturated, Alternatively at least mono-substituted C1-12 alkyl, can also be C1-10 alkyl, can also be C1-6 alkyl, can also be C1-4 hydrocarbon Base, can also be C1-12 aliphatic group, can also be C1-10 aliphatic group, can also be C1-6 aliphatic group, also It can be C1-4 aliphatic group.For example, R1, R2, R3, R4 can independently represent methyl, ethyl, n-propyl, isopropyl, just Butyl, isobutyl group, the tert-butyl group, sec-butyl etc..In some specific embodiments of the present invention, organic silicon source can be positive silicon Double (the trimethyoxysilane of sour methyl esters, tetraethyl orthosilicate, positive silicic acid propyl ester, four butyl ester of positive silicic acid, positive isopropyl silicate, 1,2- Base) a kind of or their any combination in ethane (1,2-bis (trimethoxysily) ethane, BTME).
In preparation method provided by the present invention, structure directing agent can be that this area is various suitable for preparing mesoporous material Structure directing agent, can be more specifically the various templates suitable for preparing mesoporous material in this area, the structure directing agent Surfactant type structure directing agent and on-surface-active formulation structure directing agent, the surfactant type structure can be included Directed agents can be including but not limited to cationic surface active agent, anionic surfactant, non-ionic surface active A kind of or their any combination in agent, amphoteric surfactant etc., those skilled in the art can be according to Jie of required preparation The size in Porous materials aperture selects suitable structure directing agent, and for example, using the long chain quaternary of different chain length, (C atomicity is 8-22), anion surfactant or neutral organic amine do the aperture that surfactant can obtain 2-8nm, such as document “Formation of nanosized zirconia-supported 12-tungstophosphoric acid in mesoporous silica SBA-15:A stable and versatile solid acid catalyst for Benzylation of phenol, Journal of catalysis, 2005,235：341-352”；Done using long chain quaternary Structure directing agent, can obtain the aperture of 5-8nm, such as document " Development of using High-temperature water heat treatment cholesterol biosensor with high sensitivity using dual-enzyme immobilization Into the mesoporous silica materials, Applied Surface Science, 2011,258 (5)： 1725-1732”；Do, using block copolymer, the aperture that structure directing agent can obtain 4-12nm；Using block copolymer (such as PEO-PPO-PEO block copolymer P123, F127) make structure directing agent, using High-temperature water heat treatment (as document " Synthesis of functionalized SBA-15 with ordered large pore size and its adsorption Properties of BSA, Microporous and Mesoporous materials, 2008,110：560-569 ") or Add swelling agent molecule (such as lauryl amine, TMB, triisopropylbenzene, polyvinyl alcohol, such as document " the A facile strategy of micella To synthesize spherical SBA-15 silicas by the addition of polylvinyl alcohol, Materials Letters, 2013,9：33-35 ") aperture of 10-25nm can be obtained；Tied using conventional block copolymer Structure directed agents, the low temperature synthesis of addition micella sweller can obtain the aperture of 20-50nm (as document " Spherical siliceous mesocellular foam particles for high-speed size exclusion Chromatography, Chem.Mater., 2007,19:2292-2298”).The cationic surface active agent can be example Such as, including but not limited to quaternary ammonium salt cationic surfactant CnH2n+1N(CH3)3Br (n=8-22), Gemini surfactant, CTAB、C18TAB、CTAC、C12TAC、C22TAC, cetylpyridinium chloride, TMAH and tetraethylammonium bromide, N, N- dimethyl hexadecyl amine, N, a kind of or their any combination in N- dimethyloctadecylammonium amine etc..The anionic table Face activating agent can be for example including but not limited to sodium alkyl benzene sulfonate and soap surfactant etc., such as dodecyl Benzene sulfonic acid sodium salt, the potassium of higher fatty acids, sodium, ammonium salt and tri ethanol ammonium salt, fluorine-containing surfactant C10F21COONa、 C8F17CONH(CH2)5COONa、C9F17OC6H4SO3A kind of or their any combination in K etc..The non-ionic surface is lived Property agent can be for example, including but not limited to Jeffamine D2000, F127, F108, P123, Brij30, Brij35, In Brij50, Brij65, Tx-100, Tween 20, Tween 40, Tween 60, span20, span40, span60 etc. one Plant or their any combination.The on-surface-active formulation structure directing agent can be for example including but not limited to inorganic salts Structure directing agent, D-Glucose, D-Maltose, dibenzoyl tartaric acid, dodecane, the tetradecane, hexadecane, PEO, PEG, lemon Lemon acid, malic acid, tannic acid, tartaric acid, lactic acid, oxalic acid, caprolactam, a kind of or their any group in polystyrene PS Close.More specifically, the inorganic salts structure directing agent can be various suitable for the inorganic of mesoporous material synthesis in prior art Salt structure directing agent, for example, it may be including but not limited to sodium chloride, potassium chloride, calcium chloride, sodium nitrate, potassium nitrate, sulfuric acid A kind of or their any combination in potassium, sodium sulphate etc..Those skilled in the art can be according to the usage amount of silicon source adjustment knot The consumption of structure directed agents, with molar ratio computing, silicon source can be generally 1 with the amount ratio of structure directing agent：0.0001-3, for example may be used To be 1：0.0001-0.001、1：0.001-0.01、1：0.01-0.1、1：0.1-1、1：1-1.5、1：1.5-2、1：2-2.5、1： 2.5-3.
In preparation method provided by the present invention, the solvent can select that this area is various can synthesize as mesoporous material During solvent phase solvent.The solvent can be generally water, preferably deionized water, or organic solvent, described Organic solvent can be for example a kind of including but not limited in methyl alcohol, ethanol, propyl alcohol, isopropanol, butanol etc. or they appoint Meaning combination.Those skilled in the art can select suitable solvent according to according to the species of silicon source, and for example organic silicon source can be used Organic solvent, inorganic silicon source can use inorganic solvent, it is also possible to using inorganic, organic mixed solvent.Those skilled in the art The consumption of solvent can also be adjusted according to the usage amount of silicon source, and silicon source can be generally 1 with the mass ratio of solvent：2-300,1： 10-100、1：100-200、1：200-300、1：5-190、1：10-180、1：15-170、1：20-160、1：25-150、1：30- 140、1：35-130、1：40-120、1：45-110 or 1：50-100.
In preparation method provided by the present invention, the catalyst can be various suitable for mesoporous material system from this area Standby catalyst.The catalyst can be acid catalyst, and acid catalyst can be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, second A kind of or their any combination in acid, hydrogen bromide etc..The catalyst can also be base catalyst, and the base catalyst can To be ammoniacal liquor, NaOH, potassium hydroxide, urea, monoethanolamine, TMAH (TMAOH), tetraethyl ammonium hydroxide Etc. (TEAOH) a kind of or their any combination in.Those skilled in the art can select to close according to the species of structure directing agent Suitable catalyst, for example, using can select base catalyst during cationic surfactant；Using hydrophilic group head positively charged Surfactant when can select acidic catalyst.Consumption for catalyst is not particularly limited, and can be that this area is normal The catalyst amount of rule, for example, the consumption of catalyst can allow mesoporous material precursor solution for acid, neutral or alkali Property, then for example, the consumption of catalyst can be that to make the pH of mesoporous material precursor solution be 0.5-12,0.5-1,1-2,2-3,3- 4th, 4-5,5-6,6-6.5,6.5-7,7-7.5,7.5-8,8-9,9-10,10-11 or 11-12.
In the preparation method of mesoporous composite material provided by the present invention, when doped with removing in the mesoporous material of required preparation Beyond Si, O during other elements, the material (alloy corresponding to doped chemical can be added when mesoporous material presoma is prepared Matter), make silicon source and dopant under conditions of structure directing agent, solvent are present, can be more specifically in structure directing agent, molten Under conditions of agent, catalyst are present, mesoporous material presoma is prepared.Those skilled in the art can be according to required doping Element determine corresponding dopant and its usage amount, can be for example salt or its oxide corresponding to doped chemical etc., Again for example when doped chemical is Cr, Cr (NO can be added when mesoporous material presoma is prepared3)3；Again for example, dopant Usage amount generally can according to doping of the doped chemical in silicon-based mesoporous material conversion obtain.
The purposes of mesoporous composite material
Another aspect of the present invention provides purposes of the mesoporous composite material in thermostable heat-isolating material is prepared.
Mesoporous composite material provided by the present invention has an excellent heat insulation and preservation effect, and mesoporous material and fiber and/ Or with stable composite construction between fibre, there is good heat-resistant stability and low heat conduction system under the high temperature conditions Number, can be used for preparing high-temperature heat insulation heat insulating material.Described for prepare high-temperature heat insulation heat insulating material can be will be described mesoporous Composite directly as high-temperature heat insulation heat insulating material (for example, including but not limited to when mesoporous composite material be coiled material, sheet material etc. When), or the mesoporous composite material and other materials are combined further, prepare high temperature insulating thermal insulating material Material.The high-temperature heat insulation heat insulating material is often referred to have good heat-resistant stability and low thermal conductivity at high temperature (to hot-fluid With notable resistance) material, the high temperature can be for example be not less than 450 DEG C, 700 DEG C, 1000 DEG C, 1300 DEG C, 1600 DEG C or 2000 DEG C of environment temperature；Described specifically can refer to mesoporous composite material at high temperature with good heat-resistant stability A period of time after (can be for example 0.5h, 1h, 2h, 3h, 4h, 6h, 8h, 12h, 16h, 24h, 2 days, 3 days, 4 days, 6 days, 8 My god, 10 days etc.) hardness and brittleness are nothing significant change, and/or do not occur obvious efflorescence, hole to cave in, and/or composite shrinks Rate is not more than 5%, is not more than 4%, is not more than 3%, is not more than 2% or no more than 1%；The low thermal conductivity can refer to be situated between The thermal conductivity factor of hole composite material is not higher than 0.040w/ (m k), not higher than 0.035w/ (m k), not higher than 0.030w/ (m K), it is not higher than 0.025w/ (m k), not higher than 0.020w/ (m k), not higher than 0.015w/ (m k) or is not higher than 0.010w/(m·k).According to the parameter of mesoporous composite material, those skilled in the art can determine that its high temperature insulating that can be prepared is protected Adiabator product.
As described above, the present invention is by mesoporous material and fiber composite by way of heat treatment, and further to composite wood Material is studied, so as to provide a kind of have at high temperature good heat-resistant stability and low thermal conductivity with-Si-O- The compound composite mesoporous heat-insulating heat-preserving material of Si- key, the composite construction of the composite keep stable (no obvious at high temperature Hardening, become fragile, will not efflorescence, i.e. pore structure will not cave in, composite shrinkage factor is not more than 2%), with good industrialization Prospect.
Present invention is further described below by example, but does not therefore limit the model of the application Enclose.
Each raw material used in embodiment is commercially available prod as without specified otherwise.
Measuring method used in embodiment is as follows：
The measuring method of thermal conductivity factor is with reference to ASTM C518.
The measuring method of composite shrinkage factor is with reference to ASTM C356.
Embodiment 1
Cetyl trimethylammonium bromide (CTAB) is dissolved completely in deionized water, stirring is lower add NaOH and Cab-O-Sil silica, the mixture mole consist of 1Cab-O-Sil silica：0.07CTAB：0.2NaOH： 200H2O；Autoclave is transferred to after stirring at normal temperature 1h, 90 ± 10 DEG C of hydro-thermal reactions 2 hours, precursor solution is obtained, by silicon Sour aluminum fiber mat (apparent density 0.09g/cm3, 3 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fine Dimension felt=0.3：1), be combined and fully 5h sintered after 650 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained is mesoporous Material pore volume is 0.12ml/g, and aperture is 2.6nm, and hole wall is 1.6nm, and porosity is 28.37%, changes infrared ray by fourier Spectroanalysis instrument (FTIR) detects Si-O-Si key, and FTIR analysis shows that the Si-O-Si key for not being combined silicon-based mesoporous material exists 1096cm-1There is eigen vibration absworption peak at place；After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite It is moved to 1078cm-1Place, thus prove mesoporous have strong interaction and fiber between, that is, define new Si-O-Si key. The normal temperature thermal conductivity factor of the composite mesoporous heat-barrier material of gained is 0.030w/ (m k), and 2000 DEG C of heating 1h hardness and brittleness are nothing bright Aobvious change, does not occur efflorescence, hole to cave in, and composite shrinkage factor is not more than 2%；1500 DEG C of heating 1h hardness and brittleness are nothing obvious Change, does not occur efflorescence, hole to cave in, and composite shrinkage factor is not more than 2%；1000 DEG C of heating 2h hardness and brittleness nothing substantially become Change, do not occur efflorescence, hole to cave in, composite shrinkage factor is not more than 2%；800 DEG C of heating 10d hardness and brittleness nothing substantially become Change, do not occur efflorescence, hole to cave in, composite shrinkage factor is not more than 2%.
Embodiment 2
Cetyl trimethylammonium bromide (CTAB) is dissolved completely in deionized water, stirring is lower add NaOH and TEOS, the mixture mole consist of 1TEOS：0.16CTAB：0.45NaOH：50H2O；High pressure is transferred to after stirring at normal temperature 1h Reactor, 70 ± 10 DEG C of hydro-thermal reactions 6 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/cm3, 3 μm of diameter) (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.29：1), it is combined fully after 650 DEG C sintering 5h, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 0.24ml/g, and aperture is 7nm, hole wall are 3.1nm, and porosity is 44.20%, change infrared spectrum analysis instrument (FTIR) by fourier and detect Si-O-Si Key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place；Compound Afterwards, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus prove mesoporous with There is strong interaction between fiber, that is, define new Si-O-Si key.The normal temperature heat conduction of the composite mesoporous heat-barrier material of gained Coefficient is 0.0295w/ (m k), and 2000 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；1500 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%；1000 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in, composite nothing significant change Shrinkage factor is not more than 2%；800 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite is received Shrinkage is not more than 2%.
Embodiment 3
P123 (BASF AG's product, molecular weight 5800) is dissolved completely in deionized water, stirring is lower add hydrochloric acid and TEOS, the mixture mole consist of 1TEOS：0.064P123：0.05HCl：120H2O；Shift after stirring at normal temperature 1h paramount Pressure reactor, 40 ± 10 DEG C of hydro-thermal reactions 15 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/ cm3, 3 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.28：1) after, being combined fully 1h is sintered in 1000 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 0.32ml/g, hole Footpath is 4.2nm, and hole wall is 4.8nm, and porosity is 51.36%, changes infrared spectrum analysis instrument (FTIR) detection by fourier Si-O-Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1Place has eigen vibration to absorb Peak；After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus demonstrate,proves Bright mesoporous have strong interaction and fiber between, that is, define new Si-O-Si key.The composite mesoporous heat-barrier material of gained Normal temperature thermal conductivity factor is 0.029w/ (m k), and 2000 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to collapse nothing significant change Collapse, composite shrinkage factor is not more than 2%；1500 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to collapse nothing significant change Collapse, composite shrinkage factor is not more than 2%；1000 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to collapse nothing significant change Collapse, composite shrinkage factor is not more than 2%；800 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to collapse nothing significant change Collapse, composite shrinkage factor is not more than 2%.
Embodiment 4
Hexadecyltrimethylammonium chloride (CTAC) is dissolved completely in deionized water, stirring is lower add hydrochloric acid and Na2SiO3, the mixture mole consist of 1Na2SiO3：0.5CTAC：0.06HCl：75H2O；Shift after stirring at normal temperature 1h paramount Pressure reactor, 60 ± 10 DEG C of hydro-thermal reactions 11 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/ cm3, 3 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.225：1) after, being combined fully 2h is sintered in 850 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 0.35ml/g, aperture For 12nm, hole wall is 5.3nm, and porosity is 53.60%, changes infrared spectrum analysis instrument (FTIR) by fourier and detects Si- O-Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place； After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus proves to be situated between There is strong interaction between hole and fiber, that is, define new Si-O-Si key.The normal temperature of the composite mesoporous heat-barrier material of gained Thermal conductivity factor is 0.0288w/ (m k), and 2000 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, Composite shrinkage factor is not more than 2%；1500 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, multiple Condensation material shrinkage factor is not more than 2%；1000 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；800 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%.
Embodiment 5
P123 (BASF AG's product, molecular weight 5800) is dissolved completely in deionized water, stirring is lower add hydrochloric acid and TEOS, the mixture mole consist of 1TEOS：0.05P123：0.01HCl：120H2O；High pressure is transferred to after stirring at normal temperature 1h Reactor, 60 ± 10 DEG C of hydro-thermal reactions 18 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/ cm3, 3 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.22：1) after, being combined fully 3.5h is sintered in 750 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 0.38ml/g, hole Footpath is 5.4nm, and hole wall is 3nm, and porosity is 55.64%, changes infrared spectrum analysis instrument (FTIR) by fourier and detects Si- O-Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place； After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus proves to be situated between There is strong interaction between hole and fiber, that is, define new Si-O-Si key.The normal temperature of the composite mesoporous heat-barrier material of gained Thermal conductivity factor is 0.0285w/ (m k), and 1500 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, Composite shrinkage factor is not more than 2%；1200 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, multiple Condensation material shrinkage factor is not more than 2%；1000 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；800 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%.
Embodiment 6
Cetyl trimethylammonium bromide (CTAB) is dissolved completely in deionized water, stirring is lower add NaOH and Cab-O-Sil silica, the mixture mole consist of 1Cab-O-Sil silica：0.1CTAB：0.28NaOH： 25H2O；Autoclave is transferred to after stirring at normal temperature 1h, 80 ± 10 DEG C of hydro-thermal reactions 2 hours, precursor solution is obtained, by height Silica fiber felt (SiO2Content ＞ 96%, apparent density 0.15g/cm3, 8 μm of diameter) it is soaked in (by quality in precursor solution Compare precursor solution：Fibrofelt=0.25：1), be combined and fully 3h sintered after 700 DEG C, finally give Si-O-Si composite mesoporous Heat-barrier material.Gained mesoporous material pore volume is 0.4ml/g, and aperture is 9.1nm, and hole wall is 2.1nm, and porosity is 56.90%, leads to Fourier conversion infrared spectrum analysis instrument (FTIR) detection Si-O-Si key is crossed, FTIR analysis shows, is not combined silicon-based mesoporous material Si-O-Si key in 1096cm-1There is eigen vibration absworption peak at place；After compound, the Si-O-Si key of mesoporous-fibrous composite Eigen vibration absworption peak is moved to 1078cm-1Place, thus prove mesoporous have strong interaction and fiber between, that is, define New Si-O-Si key.The normal temperature thermal conductivity factor of the composite mesoporous heat-barrier material of gained is 0.028w/ (m k), 1500 DEG C of heating 1h Hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite shrinkage factor is not more than 2%；1200 DEG C of heating 1h are hard Degree and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite shrinkage factor is not more than 2%；1000 DEG C of heating 2h hardness With brittleness nothing significant change, efflorescence, hole is not occurred to cave in, composite shrinkage factor is not more than 2%；800 DEG C of heating 10d hardness and Brittleness does not occur efflorescence, hole to cave in nothing significant change, and composite shrinkage factor is not more than 2%.
Embodiment 7
N, N- dimethyl hexadecyl amine is dissolved completely in deionized water, stirring is lower to add HBr and methyl silicate, should Mixture mole consist of 1 methyl silicate：0.3N, N- dimethyl hexadecyl amine：5.5HBr：150H2O；Stirring at normal temperature 1h After be transferred to autoclave, 40 ± 10 DEG C of hydro-thermal reactions 16 hours, obtain precursor solution, by high silica fiber felt (SiO2 Content ＞ 96%, apparent density 0.15g/cm3, 8 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fine Dimension felt=0.25：1), be combined and fully 5h sintered after 650 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained is situated between Porous materials pore volume is 0.46ml/g, and aperture is 26nm, and hole wall is 1.2nm, and porosity is 60.29%, is changed by fourier infrared Linear light spectrometer (FTIR) detects Si-O-Si key, and FTIR analysis shows that the Si-O-Si key for not being combined silicon-based mesoporous material exists 1096cm-1There is eigen vibration absworption peak at place；After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite It is moved to 1078cm-1Place, thus prove mesoporous have strong interaction and fiber between, that is, define new Si-O-Si key. The normal temperature thermal conductivity factor of the composite mesoporous heat-barrier material of gained is 0.0276w/ (m k), and 1500 DEG C of heating 1h hardness and brittleness are nothing bright Aobvious change, does not occur efflorescence, hole to cave in, and composite shrinkage factor is not more than 2%；1200 DEG C of heating 1h hardness and brittleness are nothing obvious Change, does not occur efflorescence, hole to cave in, and composite shrinkage factor is not more than 2%；1000 DEG C of heating 2h hardness and brittleness nothing substantially become Change, do not occur efflorescence, hole to cave in, composite shrinkage factor is not more than 2%；800 DEG C of heating 10d hardness and brittleness nothing substantially become Change, do not occur efflorescence, hole to cave in, composite shrinkage factor is not more than 2%.
Embodiment 8
Tween 20 (polysorbas20, traditional Chinese medicines Products, molecular weight 1227.5) is dissolved completely in deionized water, stirring Lower addition sulfuric acid and TEOS, the mixture mole consist of 1TEOS：0.02Tween 20：0.5 sulfuric acid：200H2O；Normal temperature is stirred Autoclave is transferred to after mixing 1h, 35 ± 10 DEG C of hydro-thermal reactions 20 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/cm3, 3 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt= 0.29：1), be combined and fully 6h sintered after 550 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material Pore volume is 0.67ml/g, and aperture is 4.6nm, and hole wall is 2.4nm, and porosity is 68.86%, changes infrared spectrum by fourier Analyzer (FTIR) detects Si-O-Si key, and FTIR analysis shows, is not combined the Si-O-Si key of silicon-based mesoporous material in 1096cm-1 There is eigen vibration absworption peak at place；After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus prove mesoporous have strong interaction and fiber between, that is, define new Si-O-Si key.Gained is situated between The normal temperature thermal conductivity factor of hole composite heat-insulated material is 0.0263w/ (m k), and 1000 DEG C of heating 1h hardness and brittleness nothing substantially become Change, do not occur efflorescence, hole to cave in, composite shrinkage factor is not more than 2%；900 DEG C are heated 1h hardness and brittleness nothing significant change, Efflorescence, hole is not occurred to cave in, composite shrinkage factor is not more than 2%；800 DEG C of heating 2h hardness and brittleness nothing significant change, no Generation efflorescence, hole cave in, and composite shrinkage factor is not more than 2%；750 DEG C of heating 10d hardness and brittleness are not sent out nothing significant change Fecula, hole cave in, and composite shrinkage factor is not more than 2%.
Embodiment 9
P123 (BASF AG's product, molecular weight 5800) is dissolved completely in deionized water, stirring is lower add nitric acid and TEOS, the mixture mole consist of 1TEOS：0.03P123：0.05 nitric acid：120H2O；Shift after stirring at normal temperature 1h paramount Pressure reactor, 70 ± 10 DEG C of hydro-thermal reactions 3 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/ cm3, 3 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.3：1), be combined fully after 450 DEG C of sintering 8h, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 0.71ml/g, and aperture is 6.3nm, hole wall are 3.5nm, and porosity is 70.09%, change infrared spectrum analysis instrument (FTIR) by fourier and detect Si-O- Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place；Multiple After conjunction, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus proves mesoporous There is strong interaction between fiber, that is, define new Si-O-Si key.The normal temperature of the composite mesoporous heat-barrier material of gained is led Hot coefficient is 0.026w/ (m k), and 1000 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；900 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%；800 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in, composite nothing significant change Shrinkage factor is not more than 2%；750 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite is received Shrinkage is not more than 2%.
Embodiment 10
By TX-100 (OPEO, traditional Chinese medicines Products, molecular weight be 646.86) be dissolved completely in from In sub- water, stirring is lower to add hydrochloric acid and TEOS, the mixture mole consist of 1TEOS：0.05TX-100：6 hydrochloric acid： 200H2O；Autoclave is transferred to after stirring at normal temperature 1h, 40 ± 10 DEG C of hydro-thermal reactions 12 hours, precursor solution is obtained, will High silica fiber felt (SiO2Content ＞ 96%, apparent density 0.15g/cm3, 8 μm of diameter) it is soaked in (by matter in precursor solution Amount compares precursor solution：Fibrofelt=0.31：1), be combined and fully 9h sintered after 350 DEG C, finally give Si-O-Si mesoporous multiple Close heat-barrier material.Gained mesoporous material pore volume is 0.82ml/g, and aperture is 31nm, and hole wall is 2.6nm, and porosity is 73.20%, Infrared spectrum analysis instrument (FTIR) is changed by fourier Si-O-Si key is detected, FTIR analysis shows, is not combined silicon-based mesoporous material The Si-O-Si key of material is in 1096cm-1There is eigen vibration absworption peak at place；After compound, the Si-O-Si key of mesoporous-fibrous composite Eigen vibration absworption peak be moved to 1078cm-1Place, thus prove mesoporous have strong interaction and fiber between, that is, formed New Si-O-Si key.The normal temperature thermal conductivity factor of the composite mesoporous heat-barrier material of gained is 0.0257w/ (m k), 1000 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite shrinkage factor is not more than 2%；900 DEG C of heating 1h Hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite shrinkage factor is not more than 2%；800 DEG C of heating 2h are hard Degree and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite shrinkage factor is not more than 2%；750 DEG C of heating 10d hardness With brittleness nothing significant change, efflorescence, hole is not occurred to cave in, composite shrinkage factor is not more than 2%.
Embodiment 11
P123 (BASF AG's product, molecular weight 5800) is dissolved completely in deionized water, stirring is lower add hydrochloric acid and TEOS, the mixture mole consist of 1TEOS：0.0172P123：6HCl：208.33H2O；Shift after stirring at normal temperature 1h paramount Pressure reactor, 80 ± 10 DEG C of hydro-thermal reactions 3 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/ cm3, 3 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.31：1) after, being combined fully 10h is sintered in 350 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 0.88ml/g, hole Footpath is 5.3nm, and hole wall is 2.8nm, and porosity is 74.39%, changes infrared spectrum analysis instrument (FTIR) detection by fourier Si-O-Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1Place has eigen vibration to absorb Peak；After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus demonstrate,proves Bright mesoporous have strong interaction and fiber between, that is, define new Si-O-Si key.The composite mesoporous heat-barrier material of gained Normal temperature thermal conductivity factor is 0.0254w/ (m k), and 1000 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to collapse nothing significant change Collapse, composite shrinkage factor is not more than 2%；900 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, Composite shrinkage factor is not more than 2%；800 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, multiple Condensation material shrinkage factor is not more than 2%；750 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%.
Embodiment 12
Cetyl trimethylammonium bromide (CTAB) is dissolved completely in deionized water, stirring is lower add NaOH and TEOS, the mixture mole consist of 1TEOS：0.2CTAB：0.6NaOH：72H2O；It is anti-that high pressure is transferred to after stirring at normal temperature 1h Kettle is answered, 40 ± 10 DEG C of hydro-thermal reactions 1 hour, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/cm3, directly 3 μm of footpath) (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.315：1), it is combined fully after 250 DEG C sintering 12h, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 1.02ml/g, and aperture is 2.5nm, hole wall are 2.2nm, and porosity is 77.10%, change infrared spectrum analysis instrument (FTIR) by fourier and detect Si-O- Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place；Multiple After conjunction, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus proves mesoporous There is strong interaction between fiber, that is, define new Si-O-Si key.The normal temperature of the composite mesoporous heat-barrier material of gained is led Hot coefficient is 0.0244w/ (m k), and 900 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；800 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%；750 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in, composite nothing significant change Shrinkage factor is not more than 2%；700 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite is received Shrinkage is not more than 2%.
Embodiment 13
Span-20 (Arlacel-20, traditional Chinese medicines Products, molecular weight 346.45) is dissolved completely in deionized water, stirring Lower addition oxalic acid and TEOS, the mixture mole consist of 1TEOS：0.02span-20：1 oxalic acid：120H2O；Stirring at normal temperature Autoclave is transferred to after 1h, 40 ± 10 DEG C of hydro-thermal reactions 1 hour, precursor solution is obtained, quartz fiber felt is (apparent close Degree 0.04g/cm3, 4 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.32：1), multiple Close and fully 14h is sintered after 150 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 1.12ml/g, aperture are 12nm, and hole wall is 5nm, and porosity is 78.71%, changes infrared spectrum analysis instrument by fourier (FTIR) Si-O-Si key is detected, FTIR analysis shows, is not combined the Si-O-Si key of silicon-based mesoporous material in 1096cm-1There is spy at place Levy vibration absorption peak；After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1 Place, thus prove mesoporous have strong interaction and fiber between, that is, define new Si-O-Si key.Gained is composite mesoporous The normal temperature thermal conductivity factor of heat-barrier material is 0.0228w/ (m k), and 900 DEG C of heating 1h hardness and brittleness do not occur nothing significant change Efflorescence, hole cave in, and composite shrinkage factor is not more than 2%；There is no powder nothing significant change in 800 DEG C of heating 1h hardness and brittleness Change, hole caves in, composite shrinkage factor is not more than 2%；750 DEG C heating 2h hardness and brittleness nothing significant change, do not occur efflorescence, Hole caves in, and composite shrinkage factor is not more than 2%；There is no efflorescence, hole nothing significant change in 700 DEG C of heating 10d hardness and brittleness Cave in, composite shrinkage factor is not more than 2%.
Embodiment 14
P123 (BASF AG's product, molecular weight 5800) is dissolved completely in deionized water, stirring is lower add hydrochloric acid and TEOS, the mixture mole consist of 1TEOS：0.035P123：6HCl：196H2O；It is anti-that high pressure is transferred to after stirring at normal temperature 1h Kettle is answered, 40 ± 10 DEG C of hydro-thermal reactions 21 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/cm3, 3 μm of diameter) (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.32：1), it is combined fully after 100 DEG C sintering 18h, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 1.2ml/g, and aperture is 35nm, hole wall are 5.2nm, and porosity is 79.84%, change infrared spectrum analysis instrument (FTIR) by fourier and detect Si-O- Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place；Multiple After conjunction, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus proves mesoporous There is strong interaction between fiber, that is, define new Si-O-Si key.The normal temperature of the composite mesoporous heat-barrier material of gained is led Hot coefficient is 0.022w/ (m k), and 900 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；800 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%；750 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in, composite nothing significant change Shrinkage factor is not more than 2%；700 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite is received Shrinkage is not more than 2%.
Embodiment 15
P123 (BASF AG's product, molecular weight 5800) is dissolved completely in deionized water, stirring is lower to add sodium chloride And TEOS, the mixture mole consist of 1TEOS：0.01P123：0.50NaCl：220H2O；It is transferred to after stirring at normal temperature 1h Autoclave, 40 ± 10 DEG C of hydro-thermal reactions 19 hours, precursor solution is obtained, by quartz fiber felt (apparent density 0.04g/ cm3, 4 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.33：1) after, being combined fully 20h is sintered in 90 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 1.36ml/g, aperture For 42nm, hole wall is 6.4nm, and porosity is 81.78%, changes infrared spectrum analysis instrument (FTIR) by fourier and detects Si- O-Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place； After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus proves to be situated between There is strong interaction between hole and fiber, that is, define new Si-O-Si key.The normal temperature of the composite mesoporous heat-barrier material of gained Thermal conductivity factor is 0.0215w/ (m k), and 900 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, multiple Condensation material shrinkage factor is not more than 2%；800 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；750 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%；700 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in, composite nothing significant change Shrinkage factor is not more than 2%.
Embodiment 16
Cetyl trimethylammonium bromide (CTAB) is dissolved completely in deionized water, stirring is lower add ammoniacal liquor and TEOS, the mixture mole consist of 1TEOS：0.05CTAB：0.8NH3·H2O：180H2O；It is transferred to after stirring at normal temperature 1h Autoclave, 40 ± 10 DEG C of hydro-thermal reactions 48 hours, precursor solution is obtained, by ca silicate fibre felt (apparent density 0.12g/cm3, 6 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.33：1), it is combined Fully 22h is sintered after 80 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 1.45ml/ G, aperture are 15nm, and hole wall is 9.7nm, and porosity is 82.72%, change infrared spectrum analysis instrument (FTIR) inspection by fourier Si-O-Si key is surveyed, and FTIR analysis shows, the Si-O-Si key of silicon-based mesoporous material is not combined in 1096cm-1Place has eigen vibration to inhale Receive peak；After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus Proof is mesoporous strong interaction and fiber between, that is, define new Si-O-Si key.The composite mesoporous heat-barrier material of gained Normal temperature thermal conductivity factor be 0.0208w/ (m k), 900 DEG C heating 1h hardness and brittleness nothing significant change, there is no efflorescence, hole Cave in, composite shrinkage factor is not more than 2%；800 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to collapse nothing significant change Collapse, composite shrinkage factor is not more than 2%；750 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, Composite shrinkage factor is not more than 2%；700 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, multiple Condensation material shrinkage factor is not more than 2%.
Embodiment 17
Cetyl trimethylammonium bromide (CTAB) is dissolved completely in deionized water, stirring is lower add potassium hydroxide and TEOS, the mixture mole consist of 1TEOS：0.68CTAB：0.53KOH：65H2O；High pressure is transferred to after stirring at normal temperature 1h Reactor, 100 ± 10 DEG C of hydro-thermal reactions 4 hours, precursor solution is obtained, by high silica fiber felt (SiO2Content ＞ 96%, table See density 0.15g/cm3, 8 μm of diameter) and (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.34： 1), be combined and fully 24h sintered after 500 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume For 1.6ml/g, aperture is 2.7nm, and hole wall is 7.8nm, and porosity is 84.08%, changes infrared spectrum analysis by fourier Instrument (FTIR) detects Si-O-Si key, and FTIR analysis shows, is not combined the Si-O-Si key of silicon-based mesoporous material in 1096cm-1Place has Eigen vibration absworption peak；After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus prove mesoporous have strong interaction and fiber between, that is, define new Si-O-Si key.Gained is situated between The normal temperature thermal conductivity factor of hole composite heat-insulated material is 0.0189w/ (m k), and 900 DEG C are heated 1h hardness and brittleness nothing significant change, Efflorescence, hole is not occurred to cave in, composite shrinkage factor is not more than 2%；800 DEG C of heating 1h hardness and brittleness nothing significant change, no Generation efflorescence, hole cave in, and composite shrinkage factor is not more than 2%；750 DEG C of heating 2h hardness and brittleness are not sent out nothing significant change Fecula, hole cave in, and composite shrinkage factor is not more than 2%；700 DEG C of heating 10d hardness and brittleness do not occur nothing significant change Efflorescence, hole cave in, and composite shrinkage factor is not more than 2%.
Embodiment 18
P123 (BASF AG's product, molecular weight 5800) is dissolved completely in deionized water, stirring is lower to add NH4F and TEOS, the mixture mole consist of 1TEOS：0.22P123：0.01NH4F：100H2O；High pressure is transferred to after stirring at normal temperature 1h Reactor, 90 ± 10 DEG C of hydro-thermal reactions 2 hours, precursor solution is obtained, by alumina silicate fiber felt (apparent density 0.09g/cm3, 3 μm of diameter) (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.34：1), it is combined fully after 500 DEG C sintering 24h, finally give the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 1.6ml/g, and aperture is 16nm, hole wall are 8.3nm, and porosity is 85.72%, change infrared spectrum analysis instrument (FTIR) by fourier and detect Si-O- Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place；Multiple After conjunction, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus proves mesoporous There is strong interaction between fiber, that is, define new Si-O-Si key.The normal temperature of the composite mesoporous heat-barrier material of gained is led Hot coefficient is 0.0183w/ (m k), and 900 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；800 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%；750 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in, composite nothing significant change Shrinkage factor is not more than 2%；700 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, and composite is received Shrinkage is not more than 2%.
Embodiment 19
P123 (BASF AG's product, molecular weight 5800) is dissolved completely in deionized water, stirring is lower add hydrochloric acid and TEOS, the mixture mole consist of 1TEOS：0.017P123：5HCl：180H2O；It is anti-that high pressure is transferred to after stirring at normal temperature 1h Kettle is answered, 85 ± 10 DEG C of hydro-thermal reactions 12 hours, precursor solution is obtained, by quartz fiber felt (apparent density 0.04g/cm3, directly 4 μm of footpath) (precursor solution in mass ratio is soaked in precursor solution：Fibrofelt=0.35：1), it is combined fully after 550 DEG C Sintering 3h, finally gives the composite mesoporous heat-barrier material of Si-O-Si.Gained mesoporous material pore volume is 1.96ml/g, and aperture is 14.3nm, hole wall are 2.2nm, and porosity is 86.61%, change infrared spectrum analysis instrument (FTIR) by fourier and detect Si- O-Si key, FTIR analysis show that the Si-O-Si key of compound silicon-based mesoporous material is in 1096cm-1There is eigen vibration absworption peak at place； After compound, the eigen vibration absworption peak of the Si-O-Si key of mesoporous-fibrous composite is moved to 1078cm-1Place, thus proves to be situated between There is strong interaction between hole and fiber, that is, define new Si-O-Si key.The normal temperature of the composite mesoporous heat-barrier material of gained Thermal conductivity factor is 0.0168w/ (m k), and 900 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, multiple Condensation material shrinkage factor is not more than 2%；800 DEG C of heating 1h hardness and brittleness do not occur efflorescence, hole to cave in nothing significant change, are combined Material shrinkage rate is not more than 2%；750 DEG C of heating 2h hardness and brittleness do not occur efflorescence, hole to cave in, composite wood nothing significant change Material shrinkage factor is not more than 2%；700 DEG C of heating 10d hardness and brittleness do not occur efflorescence, hole to cave in, composite nothing significant change Shrinkage factor is not more than 2%.
Embodiment 20
Jeffamine D2000 (polyetheramine, Huntsman Products, molecular weight 2000) is dissolved completely in deionization In water, stirring is lower to add ethanol and TEOS, the mixture mole consist of 1.0TEOS：0.125Jeffamine D2000： 220H2O：17EtOH；Autoclave is transferred to after stirring at normal temperature 1h, 60 ± 10 DEG C of hydro-thermal reactions 20 hours, obtain presoma Solution, by quartz fiber felt (apparent density 0.04g/cm3, 4 μm of diameter) and (presoma in mass ratio is soaked in precursor solution Solution：Fibrofelt=0.35：1), be combined and fully 4h sintered after 600 DEG C, finally give the composite mesoporous heat-barrier material of Si-O-Si. Gained mesoporous material pore volume is 2.29ml/g, and aperture is 11.9nm, and hole wall is 1.4nm, and porosity is 88.31%, by fourier Conversion infrared spectrum analysis instrument (FTIR) detection Si-O-Si key, FTIR analysis display, it is not combined the Si- of silicon-based mesoporous material O-Si key is in 1096cm-1There is eigen vibration absworption peak at place；After compound, the feature of the Si-O-Si key of mesoporous-fibrous composite is shaken Dynamic absworption peak is moved to 1078cm-1Place, thus prove mesoporous have strong interaction and fiber between, that is, define new Si-O-Si key.The normal temperature thermal conductivity factor of the composite mesoporous heat-barrier material of gained is 0.0155w/ (m k), 900 DEG C of heating 1h hardness With brittleness nothing significant change, efflorescence, hole is not occurred to cave in, composite shrinkage factor is not more than 2%；800 DEG C of heating 1h hardness and Brittleness does not occur efflorescence, hole to cave in nothing significant change, and composite shrinkage factor is not more than 2%；750 DEG C of heating 2h hardness and crisp Degree does not occur efflorescence, hole to cave in nothing significant change, and composite shrinkage factor is not more than 2%；700 DEG C of heating 10d hardness and brittleness Nothing significant change, efflorescence, hole is not occurred to cave in, composite shrinkage factor is not more than 2%.
Comparative example
Aspen company aeroge fiber felt product (XT-E) 2000 DEG C heating 1h substantially hardening, become fragile, send out Fecula, hole cave in, and Material shrinkage rate is more than 2%, and 1500 DEG C of heating 1h are substantially hardening, become fragile, and occur efflorescence, hole to cave in, material Material shrinkage factor is more than 2%, and 1200 DEG C of heating 1h are substantially hardening, become fragile, and occurs efflorescence, hole to cave in, and Material shrinkage rate is more than 2%, 1000 DEG C of heating 1h are substantially hardening, become fragile, and occur efflorescence, hole to cave in, and Material shrinkage rate is more than 2%, and 900 DEG C of heating 1h substantially become Firmly, become fragile, occur efflorescence, hole to cave in, Material shrinkage rate is more than 2%, 800 DEG C of heating 1h are substantially hardening, become fragile, occur efflorescence, Hole caves in, and Material shrinkage rate is more than 2%, and 750 DEG C of heating 2h are substantially hardening, become fragile, and occurs efflorescence, hole to cave in, Material shrinkage rate More than 2%, 700 DEG C of heating 1d are substantially hardening, become fragile, and occur efflorescence, hole to cave in, and Material shrinkage rate is more than 2%.
In sum, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe The personage for knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as All equivalent modifications for becoming or change, must be covered by the claim of the present invention.

Claims (16)

1. a kind of mesoporous composite material, including mesoporous material and fiber, the mesoporous material is silicon-based mesoporous material, the fiber It is the fiber containing silicon, compound with-Si-O-Si- key between the mesoporous material and fiber；
The aperture of mesoporous composite material intermediary Porous materials is 2-50nm；
The pore volume of mesoporous composite material intermediary Porous materials is 0.1-2.5ml/g；
The hole wall of mesoporous composite material intermediary Porous materials is 1-10nm；
The porosity of mesoporous composite material intermediary Porous materials is 20-89%.
2. a kind of mesoporous composite material as claimed in claim 1, it is characterised in that the varying aperture scope of the mesoporous material No more than 30nm, and/or the excursion of the mesoporous material hole wall is not more than 5nm.
3. a kind of mesoporous composite material as claimed in claim 2, it is characterised in that the varying aperture scope of the mesoporous material No more than 20nm, and/or the excursion of the mesoporous material hole wall is not more than 3nm.
4. a kind of mesoporous composite material as claimed in claim 1, it is characterised in that the silicon-based mesoporous material is selected from M41S system Row silicon-based mesoporous material, HMS series silicon-based mesoporous material, MSU series silicon-based mesoporous material, SBA series silicon-based mesoporous material, FDU series silicon-based mesoporous material, ZSM series silicon-based mesoporous material, KIT series silicon-based mesoporous material, the silicon-based mesoporous material of HOM series Material, FSM series silicon-based mesoporous material, AMS series silicon-based mesoporous material, IBN series silicon-based mesoporous material, TUD series silicon substrate are situated between A kind of or their any combination in Porous materials.
5. a kind of mesoporous composite material as claimed in claim 1, it is characterised in that the silicon-based mesoporous material is pure silicon substrate Mesoporous material or the silicon-based mesoporous material doped with other elements in addition to Si, O.
6. a kind of mesoporous composite material as claimed in claim 5, it is characterised in that the element of doping selected from C, B, Ti, V, Cr, One kind in Co, Mn, Fe, Ni, Zr, Cu, Ca, Cd, Sn, Ce, Sm, Pr, Nb, W, La, Al, In, Ga, Ge, Ru, Zn, Mo or it Any combination；
And/or, doping by mass percentage, is the 0.001%-40% of silicon-based mesoporous material gross mass.
7. a kind of mesoporous composite material as claimed in claim 6, it is characterised in that doping by mass percentage, is silicon The 0.1%-20% of based mesoporous material gross mass.
8. a kind of mesoporous composite material as claimed in claim 1, it is characterised in that the fiber is for obtaining after silane modified Fiber.
9. a kind of mesoporous composite material as claimed in claim 1, it is characterised in that the fiber is selected from mineral fibres, inorganic A kind of or their any combination in fiber.
10. a kind of mesoporous composite material as claimed in claim 1, it is characterised in that the quality of the mesoporous material and fiber Than for 1：0.01-50.
The preparation method of 11. mesoporous composite materials as described in claim 1-10 any claim, comprises the steps：Will Mesoporous material presoma is mixed with fiber and/or fibre, is heat-treated, and prepares the mesoporous composite material.
12. preparation methods as claimed in claim 11, it is characterised in that the temperature of the heat treatment is 25-1000 DEG C；
And/or, the mesoporous material presoma is 1 with the mass ratio of fiber and/or fibre：0.01-50.
13. preparation methods as claimed in claim 11, it is characterised in that the preparation method of the mesoporous material presoma includes Following steps：By silicon source under conditions of structure directing agent, solvent are present, mesoporous material presoma is prepared.
14. preparation methods as claimed in claim 13, it is characterised in that the silicon source is organic silicon source and/or inorganic silicon source；
And/or, the structure directing agent is surfactant type structure directing agent or on-surface-active formulation structure directing agent；
And/or, the silicon source is 1 with the mol ratio of structure directing agent：0.0001-3；
And/or, the silicon source is 1 with the mol ratio of solvent：2-300；
And/or, by silicon source under conditions of the presence of structure directing agent, solvent and catalyst, mesoporous material presoma is prepared,
Reaction system is acid, neutral or alkaline, and the pH of reaction system is 0.5-12.
15. preparation methods as claimed in claim 14, it is characterised in that the catalyst is selected from acid catalyst, base catalyst In a kind of or their any combination.
16. mesoporous composite materials as described in claim 1-10 any claim are in thermostable heat-isolating material is prepared Purposes.
CN201610844206.1A 2016-09-22 2016-09-22 A kind of mesoporous composite material and preparation method thereof and the purposes in thermostable heat-isolating material is prepared Pending CN106478053A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699106A (en) * 2016-12-27 2017-05-24 上海宥纳新材料科技有限公司 Preparation method of mesoporous composite material and high-temperature-resisting thermal insulating material prepared by preparation method
CN106747261A (en) * 2016-11-24 2017-05-31 上海宥纳新材料科技有限公司 A kind of mesoporous composite material and preparation method thereof and the purposes in resistance to middle low temperature heat-insulating heat-preserving material is prepared
CN106800402A (en) * 2016-12-27 2017-06-06 上海宥纳新材料科技有限公司 A kind of preparation method of mesoporous composite material and its resistance to middle low temperature heat-insulating heat-preserving material for preparing
CN106810194A (en) * 2016-12-27 2017-06-09 上海宥纳新材料科技有限公司 A kind of preparation method of mesoporous composite material
CN109019615A (en) * 2018-08-29 2018-12-18 华东师范大学 A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle
CN117585982A (en) * 2023-11-23 2024-02-23 浙江阿斯克建材科技股份有限公司 Preparation method of mesoporous structure calcium silicate insulation material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103011745A (en) * 2012-11-27 2013-04-03 天津大学 Silicon-dioxide aerogel heat insulation composite material and preparation method thereof
CN104326730A (en) * 2009-03-06 2015-02-04 深圳市优纳科技有限公司 Composite mesoporous material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104326730A (en) * 2009-03-06 2015-02-04 深圳市优纳科技有限公司 Composite mesoporous material
CN103011745A (en) * 2012-11-27 2013-04-03 天津大学 Silicon-dioxide aerogel heat insulation composite material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
倪星元等: "《纳米材料制备技术》", 31 December 2008, 化学工业出版社 *
化学工业出版社: "《无机非金属材料手册 下》", 31 December 2009 *
戴金辉，柳伟主编: "《无机非金属材料工学》", 31 August 2012, 哈尔滨工业大学出版社 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106747261A (en) * 2016-11-24 2017-05-31 上海宥纳新材料科技有限公司 A kind of mesoporous composite material and preparation method thereof and the purposes in resistance to middle low temperature heat-insulating heat-preserving material is prepared
CN106747261B (en) * 2016-11-24 2019-05-07 上海宥纳新材料科技有限公司 A kind of mesoporous composite material and its preparation method and its use in preparing medium and low temperature resistant thermal insulation material
CN106699106A (en) * 2016-12-27 2017-05-24 上海宥纳新材料科技有限公司 Preparation method of mesoporous composite material and high-temperature-resisting thermal insulating material prepared by preparation method
CN106800402A (en) * 2016-12-27 2017-06-06 上海宥纳新材料科技有限公司 A kind of preparation method of mesoporous composite material and its resistance to middle low temperature heat-insulating heat-preserving material for preparing
CN106810194A (en) * 2016-12-27 2017-06-09 上海宥纳新材料科技有限公司 A kind of preparation method of mesoporous composite material
CN109019615A (en) * 2018-08-29 2018-12-18 华东师范大学 A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle
CN117585982A (en) * 2023-11-23 2024-02-23 浙江阿斯克建材科技股份有限公司 Preparation method of mesoporous structure calcium silicate insulation material

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