CN105801866A - Method for preparing aluminum-containing polyborosilazane ceramic precursor - Google Patents

Method for preparing aluminum-containing polyborosilazane ceramic precursor Download PDF

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Publication number
CN105801866A
CN105801866A CN201610115186.4A CN201610115186A CN105801866A CN 105801866 A CN105801866 A CN 105801866A CN 201610115186 A CN201610115186 A CN 201610115186A CN 105801866 A CN105801866 A CN 105801866A
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hollow fiber
fiber membrane
pvdf hollow
aluminum
ceramic precursor
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CN201610115186.4A
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杜亮
马小民
冯春祥
田秀梅
李军平
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JIANGSU SAIFEI NEW MATERIAL Co Ltd
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JIANGSU SAIFEI NEW MATERIAL Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/486—Boron containing organic compounds, e.g. borazine, borane or boranyl

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a method for preparing an aluminum-containing polyborosilazane ceramic precursor. The method comprises the following specific steps of: breaking nitrogen-hydrogen bonds, reacting with an organic metal aluminum reagent to generate an aluminum-nitrogen bond, and introducing aluminum element into silicon-boron-nitrogen-carbon; adding polyborosilazane into xylene to sufficiently dissolve the polyborosilazane; adding an organic metal aluminum reagent, stirring for uniformly mixing, heating to 120 DEG C to react for 1-2 hours, and continuously heating until the mixture is boiled, and refluxing to react for 3-4 hours; and distilling xylene after the reaction is completed, and cooling to room temperature. The aluminum-containing polyborosilazane ceramic precursor is reliable in raw material source and simple in reaction process, and can be used for realizing atomic-scale uniform distribution of each element. Introduction of aluminum element can be used for enhancing the high temperature resistance of ceramics and improving the oxidation resistance of ceramic under an aerobic condition.

Description

A kind of preparation method of the PVDF hollow fiber membrane ceramic precursor containing aluminum
Technical field
The invention belongs to the preparation method of PVDF hollow fiber membrane ceramic precursor containing aluminum
Technical background
Preceramic organosilicon polymer body conversion method compared to general ceramic powder processing method, preparing the advantage on ceramic material with uniqueness, it can make each component be uniformly distributed on atomic level.This chemistry can prepare some unconventional ceramic materials, such as: fiber, coating, ceramic matric composite etc. very easily to the route of pottery, it is possible to is obtaining silicon based ceramic by synthesizing organo-silicon polymer through pyrolysis.Unbodied silicon boron nitrogen (carbon) pottery prepared by precursor pyrolysis and hot pressing and the existing a lot of reports of sial nitrogen (carbon) pottery, prepare by this method silicon boron nitrogen (carbon) pottery there is good heat stability and creep-resistant property, and sial nitrogen (carbon) pottery shows high non-oxidizability and hot corrosion resistance.And aoxidizing is the silicon-based ceramic material primary limitation that is applied to high-temperature structural material.The PVDF hollow fiber membrane of aluminum modification can obtain both combination properties after being converted into ceramic material.
A.M ü ller passes through polymer [B (C2H4Si(CH3)NH)]nToluene solution and H3Al·NMe3At room temperature reaction is prepared for Si-B-C-N aluminum ceramic precursor, ceramic yield after the ceramic precursor pyrolysis of gained is 63-71%, the oxide layer fracture occurred under high temperature oxidizing conditions relative to Si-B-C-N ceramic, the resistance to high temperature oxidation of the Si-B-C-N containing aluminum is greatly improved.
Summary of the invention
The invention aims to be incorporated in PVDF hollow fiber membrane aluminium element with atomic level, to improve further the antioxygenic property of boron silicon nitrogen pottery, the aluminum source simultaneously selected compares H3Al·NMe3It is easier to obtain, and stable.
This method course of reaction is as follows:
Wherein R1For CnH(2n+1), n=1～4, R2For CH3, C2H5
Specifically include following operating procedure:
(1) first the PVDF hollow fiber membrane of solid-state is joined with in agitating device there-necked flask, fully dissolve with dimethylbenzene.Device evacuation is led to high pure nitrogen displacement again, it is ensured that anhydrous and oxygen-free condition in device.
(3) add organometallic aluminium reagent, carry out mechanical agitation and mix up rotating speed, making two kinds of material mix homogeneously.Organic metal aluminon used is aluminium secondary butylate, aluminum isopropylate., three aluminum ethylate .s, aluminium acetylacetonate, trimethyl aluminium.
(5) begin heat to temperature 100-130 DEG C, react 2-3h, be then heated to 150 DEG C, start back flow reaction 2-3h.
(6), after question response terminates, carry out decompression and distill out dimethylbenzene,.After dimethylbenzene distillation, continue logical nitrogen until product is cooled to room temperature, i.e. can get the PVDF hollow fiber membrane containing aluminum of the solid, shaped of yellow.
Preferably, in step (1), the PVDF hollow fiber membrane of solid-state needs by xylene soluble abundant.
Preferably, described dimethylbenzene is first carried out except water processes.
Preferably, the reaction in step (3) is carried out under the conditions of anhydrous and oxygen-free.
Preferably, described PVDF hollow fiber membrane is the polymer containing N-H key.
Preferably, the organic metal aluminon described in step (2) includes aluminium secondary butylate, aluminum isopropylate., three aluminum ethylate .s, aluminium acetylacetonate or trimethyl aluminium.
Preferably, the consumption of described metallic aluminium reagent is 1wt%-10wt%.
Preferably, 3h, 2h when 150 DEG C when the reaction temperature in each stage, time are respectively 120 DEG C in step (3).
Preferably, the reaction in step (3) is that dehydrogenation coupling reaction, specially hydrogen bound to nitrogen break to form aluminum nitrogen key, and generates the reaction of sec-butyl alcohol or isopropanol or ethanol or methane gas.
Preferably, step (4) uses decompression distillation to steam dimethylbenzene, and after dimethylbenzene distills, continues logical nitrogen and cool.
Detailed description of the invention
The invention will be further described by the following examples.
Embodiment 1
(1) 100g PVDF hollow fiber membrane solid is pounded tiny bulk or powder is poured in the there-necked flask with agitating device.(2) dimethylbenzene adding 150ml makes it fully dissolve, and adds the aluminium secondary butylate of 10wt%.(3) device evacuation is then passed to high pure nitrogen.(4) open stirring and make its mix homogeneously.(5) heat temperature raising, to temperature bottle, temperature reaches 120 DEG C, reacts 2-3h.(6) continue to be heated to boiling, start back flow reaction 4h.(7) after completion of the reaction, stop being passed through nitrogen decompression distillation, after treating dimethylbenzene distillation, continue to be passed through nitrogen, be cooled to room temperature, obtain the solid of yellow.
Embodiment 2
(1) 100g PVDF hollow fiber membrane solid is pounded tiny bulk or powder is poured in the there-necked flask with agitating device.(2) dimethylbenzene adding 150ml makes it fully dissolve, and adds the aluminum isopropylate. of 10wt%.(3) device evacuation is then passed to high pure nitrogen.(4) open stirring and make its mix homogeneously.(5) heat temperature raising, to temperature bottle, temperature reaches 100 DEG C, reacts 2-3h.(6) continue to be heated to boiling, start back flow reaction 4h.(7) after completion of the reaction, stop being passed through nitrogen decompression distillation, after treating dimethylbenzene distillation, continue to be passed through nitrogen, be cooled to room temperature, obtain the solid of yellow.
Embodiment 3
(1) 100g PVDF hollow fiber membrane solid is pounded tiny bulk or powder is poured in the there-necked flask with agitating device.(2) dimethylbenzene adding 150ml makes it fully dissolve, and adds three aluminum ethylate .s of 10wt%.(3) device evacuation is then passed to high pure nitrogen.(4) open stirring and make its mix homogeneously.(5) heat temperature raising, to temperature bottle, temperature reaches 100 DEG C, reacts 2-3h.(6) continue to be heated to boiling, start back flow reaction 4h.(7) after completion of the reaction, stop being passed through nitrogen decompression distillation, after treating dimethylbenzene distillation, continue to be passed through nitrogen, be cooled to room temperature, obtain the solid of yellow.
Embodiment 4
(1) 100g PVDF hollow fiber membrane solid is pounded tiny bulk or powder is poured in the there-necked flask with agitating device.(2) dimethylbenzene adding 150ml makes it fully dissolve, and adds the trimethyl aluminium of 10wt%.(3) device evacuation is then passed to high pure nitrogen.(4) open stirring and make its mix homogeneously.(5) heat temperature raising, to temperature bottle, temperature reaches 100 DEG C, reacts 2-3h.(6) continue to be heated to boiling, start back flow reaction 4h.(7) after completion of the reaction, stop being passed through nitrogen decompression distillation, after treating dimethylbenzene distillation, continue to be passed through nitrogen, be cooled to room temperature, obtain the solid of yellow.

Claims (10)

1. the preparation method of the PVDF hollow fiber membrane ceramic precursor containing aluminum, it is characterised in that:
(1) first the PVDF hollow fiber membrane of solid-state is joined in the there-necked flask with stirring and backflow, fully dissolve with dimethylbenzene.Device evacuation is led to high pure nitrogen displacement again, it is ensured that anhydrous and oxygen-free condition in device.
(2) the described there-necked flask in step (1) adds organometallic aluminium reagent, carry out mechanical agitation and mix up rotating speed so that it is mix homogeneously.
(3) it is heated to temperature 100-130 DEG C, reacts 2-3h, be then heated to 150 DEG C, start back flow reaction 2-3h.
(4), after question response terminates, carry out decompression and distill out dimethylbenzene, after dimethylbenzene distillation, continue logical nitrogen until product is cooled to room temperature, i.e. can get the PVDF hollow fiber membrane containing aluminum of the solid, shaped of yellow.
The preparation method of a kind of PVDF hollow fiber membrane ceramic precursor containing aluminum the most according to claim 1, it is characterised in that: in step (1), the PVDF hollow fiber membrane of solid-state needs by xylene soluble abundant.
The preparation method of a kind of PVDF hollow fiber membrane ceramic precursor containing aluminum the most according to claim 1, it is characterised in that: described dimethylbenzene is first carried out except water processes.
The preparation method of a kind of PVDF hollow fiber membrane ceramic precursor containing aluminum the most according to claim 1, it is characterised in that: the reaction in step (3) is carried out under the conditions of anhydrous and oxygen-free.
The preparation method of a kind of PVDF hollow fiber membrane ceramic precursor containing aluminum the most according to claim 1, it is characterised in that: described PVDF hollow fiber membrane is the polymer containing N-H key.
The preparation method of a kind of PVDF hollow fiber membrane ceramic precursor containing aluminum the most according to claim 1, it is characterized in that: the organic metal aluminon described in step (2) includes aluminium secondary butylate, aluminum isopropylate., three aluminum ethylate .s, aluminium acetylacetonate or trimethyl aluminium.
The preparation method of a kind of PVDF hollow fiber membrane ceramic precursor containing aluminum the most according to claim 6, it is characterised in that: the consumption of described metallic aluminium reagent is 1wt%-10wt%.
The preparation method of a kind of PVDF hollow fiber membrane ceramic precursor containing aluminum the most according to claim 1, it is characterised in that: preferably, 3h, 2h when 150 DEG C when in step (3), the reaction temperature in each stage, time are respectively 120 DEG C.
The preparation method of a kind of PVDF hollow fiber membrane ceramic precursor containing aluminum the most according to claim 1, it is characterized in that: the reaction in step (3) is dehydrogenation coupling reaction, it is specially hydrogen bound to nitrogen and breaks to form aluminum nitrogen key, and generate the reaction of sec-butyl alcohol or isopropanol or ethanol or methane gas.
A kind of preparation method of the PVDF hollow fiber membrane ceramic precursor containing aluminum, it is characterised in that: step (4) uses decompression distillation to steam dimethylbenzene, and after dimethylbenzene distills, continues logical nitrogen and cool.
CN201610115186.4A 2016-03-01 2016-03-01 Method for preparing aluminum-containing polyborosilazane ceramic precursor Pending CN105801866A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107226910A (en) * 2017-07-12 2017-10-03 东南大学 A kind of method and its application that polyaluminocarbosilane precursor is prepared by silicon source of 8 hydroxyquinoline aluminums
CN107417177A (en) * 2017-06-22 2017-12-01 安徽省德邦瓷业有限公司 A kind of high-temperature Resistance Adhesives used in domestic ceramics manufacturing process

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107417177A (en) * 2017-06-22 2017-12-01 安徽省德邦瓷业有限公司 A kind of high-temperature Resistance Adhesives used in domestic ceramics manufacturing process
CN107226910A (en) * 2017-07-12 2017-10-03 东南大学 A kind of method and its application that polyaluminocarbosilane precursor is prepared by silicon source of 8 hydroxyquinoline aluminums

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