CN114891229B - Synthesis method of spinnable BN precursor with high ceramic yield - Google Patents
Synthesis method of spinnable BN precursor with high ceramic yield Download PDFInfo
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- CN114891229B CN114891229B CN202210296966.9A CN202210296966A CN114891229B CN 114891229 B CN114891229 B CN 114891229B CN 202210296966 A CN202210296966 A CN 202210296966A CN 114891229 B CN114891229 B CN 114891229B
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- 239000002243 precursor Substances 0.000 title claims abstract description 76
- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 61
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 26
- VWHCRPOEYZPVCP-UHFFFAOYSA-N ClB1N(Cl)BNBN1Cl Chemical compound ClB1N(Cl)BNBN1Cl VWHCRPOEYZPVCP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 35
- FDLQTAFYNVOAIN-UHFFFAOYSA-N ctk0i1162 Chemical group NB(N)N FDLQTAFYNVOAIN-UHFFFAOYSA-N 0.000 claims description 31
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 16
- 239000012456 homogeneous solution Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 abstract description 14
- 150000001412 amines Chemical class 0.000 abstract description 7
- 238000002074 melt spinning Methods 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- -1 Amino Borazine Chemical compound 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 125000002751 aliphatic alkane group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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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
- 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
- C04B35/583—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 based on boron nitride
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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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
- C04B35/62286—Fibres based on nitrides
- C04B35/6229—Fibres based on nitrides based on boron nitride
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- Chemical & Material Sciences (AREA)
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- Ceramic Engineering (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Polymers & Plastics (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a synthetic method of a spinnable BN precursor with high ceramic yield, which takes organic amine, primary amine and trichloroborazine as raw materials to synthesize an ABZ monomer; synthesizing a TAB monomer by taking primary amine and boron trichloride as raw materials; the ABZ monomer and the TAB monomer are subjected to a crosslinking reaction at a temperature of between 150 and 310 ℃ according to a ratio of 1.5:1 to 1:2 to prepare the spinnable polyborozane precursor containing-NR-B (NHR) -NR-flexible chains. The synthesis method provided by the invention has simple process, can be amplified in scale according to a proportion so as to be suitable for mass production, and the six-membered rings in the synthesized precursor are connected through the-NR-B (NHR) -NR-flexible chain, so that the melt spinning forming property of the precursor is greatly improved under the condition of high ceramic yield. The ceramic yield of the precursor synthesized by the method is higher than 60wt.% at 1000 ℃, the oxygen content is lower than 1wt.%, and the continuous non-broken melt spinning length can reach more than 3Km.
Description
Technical Field
The invention relates to the technical field of synthesis of organic polymer materials, in particular to a synthesis method of a spinnable BN precursor with high ceramic yield.
Background
The preparation method of BN fiber mainly comprises an inorganic precursor conversion method and an organic precursor conversion method, wherein the inorganic precursor conversion method adopts boric acid or B 2 O 3 Preparing B by high-temperature melting 2 O 3 The fiber is subjected to nitriding and high-temperature pyrolysis to obtain BN products, and the inorganic method is easy to bring a plurality of defects due to non-uniformity in the nitriding process. The organic precursor conversion method becomes a research hot point due to the designability of polymer precursor molecules, and currently, BN fiber precursors mainly comprise perhydropolyborozane and polyborozane containing boron-nitrogen six-membered rings. Among them, perhydropolyborosilazane is high in reactivity, and is easy to initiate a crosslinking reaction during melt spinning, so that melt spinning molding performance is poor. In the polyborosilazane precursor containing the rigid structure of the boron-nitrogen six-membered ring, the boron-nitrogen six-membered rings are mainly connected through B-N bonds or are connected through a-NR-group simply and flexibly, and although melt spinning can be carried out, the continuous spinning formability is still required to be further improved.
Disclosure of Invention
The invention provides a synthesis method of a high-ceramic-yield spinnable BN precursor, which is used for overcoming the defects of poor melt spinning forming performance and the like in the prior art.
In order to achieve the above object, the present invention provides a method for synthesizing a spinnable BN precursor with high ceramic yield, comprising the steps of:
(1) Preparing an ABZ monomer;
s11: dissolving trichloroborazine in an organic solvent at a temperature lower than 0 ℃ to obtain a homogeneous solution;
s12: adding organic amine while stirring the homogeneous solution at the temperature of-35-0 ℃ under inert atmosphere, continuously stirring for 1-5 h, adding primary amine, and continuously stirring for 1-5 h to obtain an ABZ monomer;
the molar ratio of the organic amine to the trichloroborazine is 0.5:1-1.5:1; the molar ratio of the primary amine to the trichloroborazine is 2:1-10:1;
(2) Preparing a TAB monomer;
s21: introducing boron trichloride into a primary amine solution at the temperature of-85 to-60 ℃ and in an inert atmosphere;
s22: stopping the cold bath after the addition is finished, stirring for 1-3 hours, and filtering to obtain a TAB monomer;
the molar ratio of the primary amine to the boron trichloride is 6:1-12:1, and the concentration of the boron trichloride in the whole reaction liquid is 10-120 g/L;
(3) Preparing BN precursor;
adding an ABZ monomer and a TAB monomer into a three-neck flask according to a molar ratio of 1.5:1-1:2, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 1-24 h at 150-310 ℃, and cooling to room temperature to obtain a BN precursor containing a-NR-B (NHR) -NR-flexible chain;
the ABZ represents an aminocycloborazine; the TAB represents a triaminoborane.
In order to achieve the above purpose, the invention also provides a spinnable BN precursor with high ceramic yield, which is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a synthetic method of a spinnable BN precursor with high ceramic yield, which takes organic amine, primary amine and trichloroborazine as raw materials to synthesize an Amino Borazine (ABZ) monomer; synthesizing a Triaminoborane (TAB) monomer by taking primary amine and boron trichloride as raw materials; and (3) carrying out crosslinking reaction on the ABZ monomer and the TAB monomer according to the proportion of 1:5-5:1 at the temperature of 150-310 ℃ to prepare the spinnable polyborozane precursor containing-NR-B (NHR) -NR-flexible chains. The synthesis method provided by the invention has simple process, can be amplified in scale according to a proportion so as to be suitable for industrial production, and the six-membered rings in the synthesized precursor are connected through the-NR-B (NHR) -NR-flexible chain, so that the melt spinning forming property of the precursor is greatly improved under the condition of high ceramic yield. The ceramic yield of the precursor synthesized by the method is higher than 60wt.%, the oxygen content is lower than 1wt.%, the continuous spinning length is higher than 3Km, and the diameter of the precursor is 5-25 mu m.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a precursor containing flexible chains prepared in example 1;
FIG. 2 is a thermogravimetric plot of the flexible chain-containing precursor prepared in example 1;
FIG. 3 is a SEM photograph of BN fibrils prepared by spinning a flexible chain-containing precursor prepared in example 1;
FIG. 4 is a photograph of a spun yarn containing a flexible chain precursor prepared in example 1;
FIG. 5 is an optical photograph of the flexible chain-containing precursor prepared in example 1.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the technical solutions, and when the technical solutions are contradictory or cannot be implemented, the combination of the technical solutions should be considered as not existing, and not falling within the scope of protection claimed by the present invention.
The drugs/reagents used are all commercially available without specific description.
The invention provides a synthesis method of a spinnable BN precursor with high ceramic yield, which comprises the following steps:
(1) Preparing an ABZ monomer;
s11: dissolving trichloroborazine in an organic solvent at a temperature below 0deg.C to obtain a homogeneous solution.
S12: adding organic amine while stirring the homogeneous solution at-35-0 ℃ under inert atmosphere, continuously stirring for 1-5 h, adding primary amine, and continuously stirring for 1-5 h to obtain the ABZ monomer.
The molar ratio of the organic amine to the trichloroborazine is 0.5:1-1.5:1; the molar ratio of the primary amine to the trichloroborazine is 2:1-10:1.
(2) Preparing a TAB monomer;
s21: introducing boron trichloride into a primary amine solution at the temperature of between-85 and-60 ℃ and in an inert atmosphere to perform acid-base neutralization reaction;
s22: stopping the cold bath after the addition is finished, stirring for 1-3 hours, and filtering to obtain a TAB monomer;
the molar ratio of the primary amine to the boron trichloride is 6:1-12:1, and the concentration of the boron trichloride in the whole reaction liquid is 10-120 g/L.
(3) Preparing BN precursor;
adding an ABZ monomer and a TAB monomer into a three-neck flask according to a molar ratio of 1.5:1-1:2, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 1-24 h at 150-310 ℃, and cooling to room temperature to obtain a BN precursor containing a-NR-B (NHR) -NR-flexible chain;
the ABZ represents an aminocycloborazine; the TAB represents a triaminoborane.
The whole preparation process is carried out under anhydrous and anaerobic conditions.
Preferably, in step (1), the concentration of trichloroborazine in the homogeneous solution is from 5 to 60g/L.
Preferably, in step (1), the organic solvent is at least one of toluene, xylene, dichlorobenzene and n-pentane.
Preferably, in step (1), the organic amine is a primary or secondary amine of formula R 1 -NH 2 Or R is 1 -NH-R 2 ，R 1 、R 2 All are aliphatic alkyl groups or phenyl groups with molecular chains of 1-5 carbon atoms.
Preferably, in steps (1) and (2), the primary amine is of the formula H 2 N-R 1 ，R 1 Is aliphatic alkyl or phenyl with 1-5 carbon atoms in molecular chain.
Preferably, in step (2), the solvent of the primary amine solution is an organic solvent, and the organic solvent is at least one of toluene, xylene, dichlorobenzene and n-pentane.
Preferably, in the step (3), the temperature of the evaporated solvent is 60 to 100 ℃.
Preferably, in the steps (1) to (3), the inert atmosphere is nitrogen or argon.
Preferably, the reaction formula of step (3) is:
wherein R is 1 、R 2 、R 3 All represent an aliphatic alkane radical or phenyl radical of 1 to 5 carbon atoms, R 4 Represents an aliphatic alkane group or phenyl group having 1 to 3 carbon atoms.
The invention also provides a spinnable BN precursor with high ceramic yield, which is prepared by the preparation method.
Example 1
The embodiment provides a synthesis method of a spinnable BN precursor with high ceramic yield, which comprises the following steps:
(1) Preparing an ABZ monomer;
dissolving trichloroborazine in toluene at a temperature lower than-20 ℃ to prepare a homogeneous solution with a concentration of 30g/L, adding n-propylamine while stirring the homogeneous solution at the temperature of-35 ℃ under the protection of inert atmosphere, wherein the molar ratio of the n-propylamine to the trichloroborazine is 1:1, continuously stirring for 5 hours, adding methylamine, and continuously stirring for 5 hours, wherein the molar ratio of the methylamine to the trichloroborazine is 2:1, so as to obtain the ABZ monomer.
(2) Preparing a TAB monomer;
slowly introducing boron trichloride into methylamine/toluene at the temperature of-85 ℃ under an inert environment, wherein the molar ratio of methylamine to boron chloride is 6:1, the concentration of boron trichloride in the total solution is 120g/L, stopping the cold bath after the addition is finished, continuously stirring for 3 hours, and filtering to obtain the TAB monomer.
Methylamine/toluene: the solute is methylamine and the solvent is toluene.
(3) Preparing BN precursor;
adding the ABZ monomer and the TAB monomer into a three-neck flask according to a molar ratio of 1:1, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 6 hours at 220 ℃, and cooling to room temperature to obtain a semitransparent polyborosilazane precursor (shown in figure 5) containing-NR-B (NHR) -NR-flexible chains, wherein the softening point is 71-109 ℃.
FIG. 1 is an infrared spectrum of a precursor containing a flexible chain prepared in this example, from which it can be seen that the precursor is at 1400cm -1 There is obvious BN six-membered ring stretching vibration peak at 808cm -1 There is a sharp bending vibration peak of the flexible chain BN.
FIG. 2 is a thermogravimetric plot of the flexible chain-containing precursor prepared in this example, showing a ceramic yield of 60.9wt.% at 1000℃and 52.5wt.% at 1500 ℃.
Fig. 3 is an SEM photograph of fibrils obtained by spinning the precursor containing flexible chains prepared in this example, and it can be seen from the figure that the prepared BN fibers have a uniform diameter, smooth fiber surfaces, and no wrinkles, and are excellent fibrils.
Fig. 4 is a photograph of the precursor spinning of this example, showing that the fiber has good toughness and spinning formability.
The ceramic yield of the polyborosilazane precursor synthesized by the embodiment is 60.9%, and the continuous spinning length can reach 3.3Km.
Example 2
The embodiment provides a synthesis method of a spinnable BN precursor with high ceramic yield, which comprises the following steps:
(1) Preparing an ABZ monomer;
dissolving trichloroborazine in toluene at a temperature lower than-20 ℃ to prepare a homogeneous solution with a concentration of 60g/L, adding n-propylamine with a molar ratio of 0.5:1 under the protection of inert atmosphere at 0 ℃, continuously stirring for 5 hours, adding methylamine with a molar ratio of 2:1, and continuously stirring for 5 hours to obtain the ABZ monomer.
(2) Preparing a TAB monomer;
as in example 1.
(3) Preparing BN precursor;
adding an ABZ monomer and a TAB monomer into a three-neck flask according to a molar ratio of 1:1, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 12 hours at 150 ℃, and cooling to room temperature to obtain a semitransparent polyborosilazane precursor containing-NR-B (NHR) -NR-flexible chains, wherein the softening point is 50-68 ℃.
The ceramic yield of the polyborosilazane precursor synthesized by the embodiment is 50.19 percent, and the continuous spinning length can reach 3.6Km.
Example 3
The embodiment provides a synthesis method of a spinnable BN precursor with high ceramic yield, which comprises the following steps:
(1) Preparing an ABZ monomer;
dissolving trichloroborazine in toluene at a temperature lower than-20 ℃ to prepare a homogeneous solution with a concentration of 60g/L, adding n-propylamine with a molar ratio of 1:1 under the protection of inert atmosphere at-10 ℃ while stirring, continuously stirring for 5h, adding methylamine with a molar ratio of 2:1, and continuously stirring for 5h to obtain the ABZ monomer.
(2) Preparing a TAB monomer;
slowly introducing boron trichloride into methylamine/toluene at the temperature of-85 ℃ under an inert environment, wherein the molar ratio of methylamine to boron chloride is 12:1, the concentration of boron trichloride in the total solution is 120g/L, stopping the cold bath after the addition, continuously stirring for 1h, and filtering to obtain the TAB monomer.
(3) Preparing BN precursor;
adding an ABZ monomer and a TAB monomer into a three-neck flask according to a molar ratio of 1.5:1, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 6 hours at 230 ℃, and cooling to room temperature to obtain a semitransparent polyborosilazane precursor containing-NR-B (NHR) -NR-flexible chains, wherein the softening point is 92-119 ℃.
The ceramic yield of the polyborosilazane precursor synthesized by the embodiment is 62.58%, and the continuous spinning length can reach 3.1Km.
Example 4
The embodiment provides a synthesis method of a spinnable BN precursor with high ceramic yield, which comprises the following steps:
(1) Preparing an ABZ monomer;
dissolving trichloroborazine in toluene at a temperature lower than-20 ℃ to prepare a homogeneous solution with a concentration of 30g/L, adding n-propylamine with a molar ratio of 1:1 under the protection of inert atmosphere at-10 ℃ while stirring, continuously stirring for 5h, adding methylamine with a molar ratio of 2:1, and continuously stirring for 5h to obtain the ABZ monomer.
(2) Preparing a TAB monomer;
slowly introducing boron trichloride into methylamine/toluene at-60 ℃ under an inert environment, wherein the molar ratio of methylamine to boron chloride is 12:1, the concentration of boron trichloride in the total solution is 60g/L, stopping the cold bath after the addition, continuously stirring for 3h, and filtering to obtain the TAB monomer.
(3) Preparing BN precursor;
adding an ABZ monomer and a TAB monomer into a three-neck flask according to a molar ratio of 1:2, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 12 hours at 220 ℃, and cooling to room temperature to obtain a semitransparent polyborosilazane precursor containing-NR-B (NHR) -NR-flexible chains, wherein the softening point is 80-105 ℃.
The ceramic yield of the polyborosilazane precursor synthesized by the embodiment is 60.66 percent, and the continuous spinning length can reach 3Km.
Example 5
The embodiment provides a synthesis method of a spinnable BN precursor with high ceramic yield, which comprises the following steps:
(1) Preparing an ABZ monomer;
dissolving trichloroborazine in toluene at a temperature lower than-20 ℃ to prepare a homogeneous solution with a concentration of 60g/L, adding n-propylamine with a molar ratio of 1:1 under the protection of inert atmosphere at-10 ℃ while stirring, continuously stirring for 5h, adding methylamine with a molar ratio of 2:1, and continuously stirring for 5h to obtain the ABZ monomer.
(2) Preparing a TAB monomer;
slowly introducing boron trichloride into methylamine/toluene at the temperature of-85 ℃ under an inert environment, wherein the molar ratio of methylamine to boron chloride is 6:1, the concentration of boron trichloride in the total solution is 120g/L, stopping the cold bath after the addition is finished, continuously stirring for 3 hours, and filtering to obtain the TAB monomer.
(3) Preparing BN precursor;
adding an ABZ monomer and a TAB monomer into a three-neck flask according to a molar ratio of 1:1, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 2 hours at 240 ℃, and cooling to room temperature to obtain a semitransparent polyborosilazane precursor containing-NR-B (NHR) -NR-flexible chains, wherein the softening point is 85-110 ℃.
The ceramic yield of the polyborosilazane precursor synthesized by the embodiment is 62.60 percent, and the continuous spinning length can reach 3.2Km.
Example 6
This example provides a method for synthesizing spinnable BN precursor with high ceramic yield, and compared with example 5, the crosslinking reaction temperature in step (3) is set to 240 and the time is 6 hours, so as to obtain the opaque polyborosilazane precursor containing-NR-B (NHR) -NR-flexible chains, and the softening point is 103-137 ℃.
The ceramic yield of the polyborosilazane precursor synthesized by the embodiment is 63.20%, and the continuous spinning length can reach 3.02Km.
Example 7
This example provides a method for synthesizing spinnable BN precursor with high ceramic yield, and compared with example 5, the crosslinking reaction temperature in step (3) is set to 260 and the time is 6 hours, so as to obtain the opaque polyborosilazane precursor containing-NR-B (NHR) -NR-flexible chains, and the softening point is 121-163 ℃.
The ceramic yield of the polyborosilazane precursor synthesized by the embodiment is 65.08%, and the continuous spinning length can reach 3.1Km.
Example 8
This example provides a method for synthesizing spinnable BN precursor with high ceramic yield, and compared with example 5, the organic solvents in steps (1) and (2) are changed from toluene to dichlorobenzene to obtain pale yellow resin-like polyborozane precursor containing-NR-B (NHR) -NR-flexible chains, and the softening point is 76-123 ℃.
The ceramic yield of the polyborosilazane precursor synthesized by the embodiment is 61.67 percent, and the continuous spinning length can reach 3.2Km.
Example 9
The embodiment provides a synthesis method of a spinnable BN precursor with high ceramic yield, which comprises the following steps:
(1) Preparing an ABZ monomer;
dissolving trichloroborazine in dimethylbenzene at a temperature lower than-20 ℃ to prepare a homogeneous solution with a concentration of 5g/L, adding dimethylamine with a molar ratio of dimethylamine to trichloroborazine of 1:1 under the protection of inert atmosphere at-10 ℃ and stirring, continuously stirring for 1h, adding methylamine with a molar ratio of methylamine to trichloroborazine of 10:1, and continuously stirring for 1h to obtain the ABZ monomer. (2) preparing a TAB monomer;
slowly introducing boron trichloride into methylamine/dimethylbenzene at the temperature of-70 ℃ under an inert environment, wherein the molar ratio of methylamine to boron chloride is 9:1, the concentration of boron trichloride in the total solution is 10g/L, stopping the cold bath after the addition, continuously stirring for 2 hours, and filtering to obtain the TAB monomer.
(3) Preparing BN precursor;
adding the ABZ monomer and the TAB monomer into a three-neck flask according to the molar ratio of 1.2:1, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 1h at the temperature of 310 ℃, and cooling to room temperature to obtain a semitransparent polyborosilazane precursor containing-NR-B (NHR) -NR-flexible chains.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the description of the present invention and the accompanying drawings or direct/indirect application in other related technical fields are included in the scope of the invention.
Claims (4)
1. The synthesis method of the spinnable BN precursor with high ceramic yield is characterized by comprising the following steps of:
(1) Preparing an ABZ monomer;
dissolving trichloroborazine in toluene at a temperature lower than-20 ℃ to prepare a homogeneous solution with a concentration of 60g/L, stirring the homogeneous solution at the temperature of-10 ℃ under the protection of inert atmosphere, adding n-propylamine while stirring the homogeneous solution, wherein the molar ratio of the n-propylamine to the trichloroborazine is 1:1, continuously stirring for 5 hours, adding methylamine, and continuously stirring for 5 hours, wherein the molar ratio of the methylamine to the trichloroborazine is 2:1, so as to obtain an ABZ monomer;
(2) Preparing a TAB monomer;
introducing boron trichloride into methylamine/toluene at the temperature of-85 ℃ under inert atmosphere, wherein the molar ratio of methylamine to boron chloride is 6:1, the concentration of boron trichloride in the total solution is 120g/L, stopping the cold bath after the charging is finished, continuously stirring for 3 hours, and filtering to obtain a TAB monomer;
(3) Preparing BN precursor;
adding an ABZ monomer and a TAB monomer into a three-neck flask according to a molar ratio of 1:1, evaporating the solvent under the protection of inert atmosphere, performing a crosslinking reaction for 6 hours at 260 ℃, and cooling to room temperature to obtain an opaque polyborosilazane precursor containing-NR-B (NHR) -NR-flexible chains, wherein the softening point is 121-163 ℃;
the ABZ represents an aminocycloborazine; the TAB represents a triaminoborane.
2. The method according to claim 1, wherein in the step (3), the temperature of the evaporated solvent is 60 to 100 ℃.
3. The method of claim 1, wherein in steps (1) to (3), the inert atmosphere is nitrogen or argon.
4. A spinnable BN precursor with high ceramic yield, prepared by the preparation process of any one of claims 1 to 3.
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