CN105837818A - Synthesizing and curing methods for main-chain benzoxazine containing carborane - Google Patents
Synthesizing and curing methods for main-chain benzoxazine containing carborane Download PDFInfo
- Publication number
- CN105837818A CN105837818A CN201610327062.2A CN201610327062A CN105837818A CN 105837818 A CN105837818 A CN 105837818A CN 201610327062 A CN201610327062 A CN 201610327062A CN 105837818 A CN105837818 A CN 105837818A
- Authority
- CN
- China
- Prior art keywords
- carborane
- chain type
- backbone chain
- type benzoxazine
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses synthesizing and curing methods for main-chain benzoxazine containing carborane. The synthesizing method comprises the steps that carborane diphenol, paraformaldehyde, diamine and a solvent are added into a reaction system, the temperature is raised to 70-90 DEG C, a reaction is carried out for 5-30 h, and main-chain benzoxazine containing carborane is obtained, wherein a mixed solution of methylbenzene and ethyl alcohol serves as the solvent. According to the synthesizing method, materials are added at one step, and thus operation is convenient; besides, the reaction temperature is small in fluctuation and easy to control, post-treatment is easy, and the yield is high. The product prepared with the synthesizing method can be cured when directly heated in air, the curing process is very simple, and no strict pollution control measure is needed. A cured product has good heat stability and a high high-temperature carbon yield, and can be used for research of high-temperature resisting materials.
Description
Technical field
The present invention relates to boron-containing compound field, relate generally to a kind of backbone chain type Benzoxazine Han carborane
Synthesis and curing.
Background technology
Carborane is a kind of polyhedral compound being made up of boron, hydrogen, three kinds of elements of carbon, is generally divided into
Open and closed, the most open have a nido and netted, and closed cage of typically refering in particular to,
Cage construction also had 12 hydrogen atoms to form by two carbon atoms and ten boron atoms positive two
Decahedron.The carborane quantity of this caged is most the most stable, be synthesis heat-proof macromolecule material
One of important raw material, therefore the carborane of general indication is and has icosahedron cage construction
Two carbon generation-enclosed-ten diborane (C2B10H12).Carborane has three kinds of isomers, i.e. 1,2-carbon boron
Alkane, 1,7-carborane and 1,12-carborane, correspondence position is respectively ortho position, meta and contraposition.Three kinds
Isomers at high temperature can occur rearrangement reaction: ortho position carborane is heated to 475 DEG C of rearrangements and obtains
Meta carborane, continues to be heated to 650 DEG C of available para-position carbon borines.
Carborane as the special chemical substance of a kind of space structure, cage structure make it have with commonly
The physicochemical properties that boron hydride is different with alkyl borohydride.Close relative to other hydroboration
Thing, the cage construction of carborane makes it have the highest heat endurance and chemical stability, even if
In the presence of 700 DEG C of high temperature or oxidant, strong bronsted lowry acids and bases bronsted lowry, the character of carborane or quite stable.
Its cage construction has and is similar to the super armaticity that three-dimensional phenyl ring is the same, the electron deficient of carborane system
Property make adjacent key degree of ionization increase, stability increase.On the other hand, the huge body of cagelike structure
Long-pending organic segment to polymer can play good shielding action, high-polymer molecular can be stoped tight simultaneously
Solid matter arranges, and plays internal plasticization, improves the processing characteristics of polymer.Additionally due to main key
Structure is carbon boron key, and carborane also has preferable resistance to water and stable chemical resistance.
According to molecular orbital theory, two hydrogen atoms that carbon atom is carried have certain lewis acid
Property, generally also mean that there is bigger activity, it is easy to anti-with alkaline reagent generation deprotonation
Should obtain nucleophile, this nucleophilic physical efficiency is reacted with electrophilic reagent further.Without complicated radical protection
Reaction just can occur substitution reaction on carbon, and does not destroy the cage structure of carborane, for carborane
Molecule introduces polymer and provides an effective way.Carborane as raw material first with butyl lithium to it
Process forms lithium salts, and then lithium salts and paraiodoanisole react formation methoxyphenyl substituted carbon boron
Alkane, and then react with pyridine hydrochloride and obtain carborane bis-phenol.The special structure of carborane makes it possess
The highest chemical stability, heat endurance and hypotoxicity, and the high polymer containing carborane, show equally
Go out corresponding excellent properties.
The upper functional group of C substituted carborane derivative synthetic method, except lithium salts method of substitution another kind is
Alkynes addition process.Alkynes addition process be by acetylene and replaced acetylene with decaborane complex compound at aromatic hydrocarbon solvent
The method of carborane derivative is prepared in middle reaction.The method is applicable to replaced acetylene without amino, hydroxyl
And the addition reaction of epoxide group etc., this is owing to decaborane is in the compound containing this kind of polar group
Can occur self to disintegrate, cause addition reaction cannot be carried out.
Can be the most anti-with other material as raw material by reacting the carborane derivative obtained above
Should obtain multiple material, the introducing of carborane significantly improves thermal stability and the carbon residue of these materials
Rate.
Carborane and derivative thereof can pass through the multiple detection means such as nuclear-magnetism, infrared and mass spectrum and characterize.As1In H H NMR spectroscopy, on boron cage there is wide short nuclear magnetic resonance peak in 0-3ppm scope in hydrogen；11B H NMR spectroscopy
Formant is there is in middle boron cage in-5 to-15ppm displacement range；2600cm in infrared spectrum-1Left and right
There is obvious B-H stretching vibration peak at place.
And for containing the heat deflection mechanism of carborane polymer under high temperature, the most all fail to obtain very
Good explanation, has been reported that when correlative study works also, by infrared, and elementary analysis and thermogravimetric analyzer
Find Deng analytical and testing instrument research, for containing carborane polymer, when temperature is less than 200 DEG C,
Most weightlessness comes from untreated volatile matter completely and the poor group of part heat resistance, when
When temperature slowly rises, can be of equal value along with B-H, B-B, B-O-B and B-C in carborane group
The change of key because along with the rising of temperature, the B-H key in carborane group easily and chemical oxygen,
I.e. oxygen in functional group or oxygen and moisture reacts, and forms B-O-B key and B-B key, even may be used
Can be B-C key, thus the polymer network structure defining three-dimensional is combined closely, due to thermally-stabilised
The appearance of macromolecular network system, therefore the free radical of generation is difficult to flee from from cage structure, experienced by
The process of one secondary restructuring, it is suppressed that further polymer degradation processes, and this contains B-O knot
The crosslinked polymer network of structure, is the main cause causing substantial amounts of coking residue.
Backbone chain type Benzoxazine is to be obtained through condensation reaction by bis-phenol, formaldehyde and diamines, the number of polymer
Average molecular weight is between 1000-10000, from the point of view of current research situation, and backbone chain type Benzoxazine
Not only there is the excellent properties of traditional Benzoxazine: water absorption rate is low；Carbon yield is high；Body in solidification process
Long-pending shrinkage factor is substantially zeroed, even there will be slight expansion；Solidification process heats without catalyst
Carry out；Poisonous accessory substance etc. is not discharged during solidification；Simultaneously because its higher molecular weight overcomes biography
System Benzoxazine is difficult to the feature of film forming；Based on these advantages, backbone chain type Benzoxazine Aero-Space,
The high-tech sectors such as microelectronics have broad application prospects.Although traditional Benzoxazine has so
Many premium properties, but superhigh temperature resistant aspect is needed to make some improvement and widens its application neck
Territory.In view of the resistance to elevated temperatures excellent containing carborane polymer, therefore carborane is introduced backbone chain type benzene
And piperazine system, improve its resistance to elevated temperatures further.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of main chain Han carborane
The synthesis of type Benzoxazine and curing, it is desirable to provide a kind of new carborane backbone chain type Benzoxazine
Preparation method, carborane bis-phenol, paraformaldehyde and diamines react and form the main chain Han carborane
Type Benzoxazine, then directly heats solidification and obtains having consolidating of the thermally-stabilised and contour performance of thermal oxidation stability
Change product.
Technical scheme is as follows:
A kind of synthetic method containing carborane backbone chain type Benzoxazine, wherein, comprises the following steps:
Carborane diphenol, paraformaldehyde, diamines, solvent are added in reaction system, is warming up to 70-90
DEG C, reaction 5-30h obtains containing carborane backbone chain type Benzoxazine；
Wherein, solvent is the mixed liquor of toluene and ethanol.
The described synthetic method containing carborane backbone chain type Benzoxazine, wherein, carborane diphenol is
M-carborane bis-phenol, p-carborane bis-phenol or o-carborane bis-phenol.
The described synthetic method containing carborane backbone chain type Benzoxazine, wherein, diamines be hexamethylene diamine,
4,4-MDA or 4,4-DADPS.
The described synthetic method containing carborane backbone chain type Benzoxazine, wherein, toluene and the body of ethanol
Long-pending ratio is (2-3): 1.
The described synthetic method containing carborane backbone chain type Benzoxazine is wherein, carborane diphenol, many
Polyformaldehyde, the mol ratio of diamines are 1:(4-4.5): 1.
The described synthetic method containing carborane backbone chain type Benzoxazine, wherein, further comprising the steps of:
To instill in the absolute methanol solution being stirred continuously containing carborane backbone chain type Benzoxazine, it is heavy to stand
Shallow lake 24-48h；
Suction filtration, collects sediment, 40 DEG C of vacuum drying 3-5h.
A kind of curing containing carborane backbone chain type Benzoxazine, wherein, described containing carborane main chain
Type Benzoxazine uses method as above to prepare, and its curing comprises the following steps:
Solidification 2-4h at carborane backbone chain type Benzoxazine is placed in 180-260 DEG C will be contained.
Beneficial effect: the synthetic method containing carborane backbone chain type Benzoxazine of the present invention, with carborane
Bis-phenol, paraformaldehyde and diamines are raw material, and toluene/ethanol is that solvent obtains.This synthetic method excellent
Point includes: (1) one step charging, it is simple to operation；(2) reaction temperature fluctuation is little, it is easy to control；(3)
Post processing is simple；(4) productivity is high.It addition, use the preparation-obtained product of this synthetic method at sky
Directly heating the most curable in gas, solidification process the most simply need not strict pollution control measures.
Cured product has good heat endurance and high temperature carbon yield, can be used for the research of exotic material.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart that the present invention contains carborane backbone chain type Benzoxazine.
Detailed description of the invention
The present invention provides a kind of synthesis containing carborane backbone chain type Benzoxazine and curing, for making this
Purpose, technical scheme and the effect of invention are clearer, clear and definite, the most detailed to the present invention below
Explanation.Should be appreciated that specific embodiment described herein, and need not only in order to explain the present invention
In limiting the present invention.
A kind of synthesis containing carborane backbone chain type Benzoxazine provided by the present invention and curing, institute
Stating the backbone chain type Benzoxazine containing carborane is with 1:(4-4.5 by carborane diphenol, paraformaldehyde, diamines): 1
Ratio obtain through condensation reaction, the introducing of carborane structure can improve gained backbone chain type Benzoxazine
Heat endurance, thus expand they application in hot environment field.
Specifically, the described synthetic method containing carborane backbone chain type Benzoxazine, synthetic route such as Fig. 1
Shown in, comprise the following steps:
The first step, to the 100ml there-necked flask equipped with magnetic stirring apparatus, thermometer and reflux condensing tube
Middle addition mol ratio carborane diphenol: paraformaldehyde: diamines=1:(4-4.5): Isosorbide-5-Nitrae ml toluene, 2ml
Ethanol；
Second step, installs reflux, temperature is slowly raised 70-90 DEG C, after reaction 5-30h
Terminate reaction；
3rd step, instills product in the 80ml absolute methanol solution being stirred continuously, staticly settles
24-48h；
4th step, G4 sand core funnel suction filtration, sediment is collected, 40 DEG C of vacuum drying 3-5h.
The molecular weight containing carborane backbone chain type Benzoxazine obtained in aforementioned manners and distribution thereof are by instead
Control between Ying Shi.
In the first step, described carborane bis-phenol is the carborane bis-phenol in formula (1), for m-carborane
Bis-phenol, p-carborane bis-phenol or o-carborane bis-phenol.Diamines is hexamethylene diamine, 4,4-diaminourea hexichol first
Alkane or 4,4-DADPS.
M-carborane bis-phenol can be obtained after being reacted with paraiodoanisole by the m-carborane of double lithiumations
Product react with alkali again and obtain (neat Shicheng etc., " synthesis of carborane phenolic resin and performance study ",
Aeronautical material journal, 34 (1), 46 (2014)).P-carborane bis-phenol same methods obtains.As for
O-carborane bis-phenol is impracticable owing to having bigger steric hindrance above method.O-carborane bis-phenol
Reacted with corresponding alkynes by decaborane and obtain (Vinogradova S V et al., " Polymers with
arylenedicarbadodecaborane fragments in the chain”,Russian Chemical
Reviews,64(4),365(1995))。
In second step, for well-chosen solvent.Polar solvent reacts, the dielectric constant of solvent
The cyclization of piperazine ring there is is considerable influence, and reacts in non-polar solven, the dielectric constant of solvent
Affect the least, simultaneously because non-polar solven and aqueous solution split-phase, promote the carrying out of reaction and reduce
Piperazine ring open loop forms dimer or the chance of oligomer, thus can get the benzo of higher degree
Piperazine.When chloroform, dioxane, dimethylbenzene make solvent, after reaction, state is not homogeneous system, for
Guarantee reaction can occur under homogeneous phase condition, and the solvent finally determined in the present invention is volume ratio first
Benzene: ethanol=(2-3): the mixed solvent of 1.
In 3rd step, for post-processing step.In order to obtain containing of the narrower HMW of molecular weight distribution
Carborane backbone chain type Benzoxazine, utilizes absolute methanol to precipitate 48h process after the completion of reaction.
The present invention provides the solidification containing carborane backbone chain type Benzoxazine using said method synthesis
Method, comprises the following steps:
The backbone chain type Benzoxazine containing carborane directly post processing obtained is placed in air dry oven,
Solidify 2-4h at 180-260 DEG C, obtain brown cured product afterwards.
The advantage of synthesis and curing that the present invention contains carborane backbone chain type Benzoxazine includes: (1)
One step charging, it is simple to operation；(2) reaction temperature fluctuation is little, it is easy to control；(3) post processing letter
Single；(4) productivity is high；(5) solidification process that product is follow-up is simple；(6) solidification resin has
Good heat endurance.
Below by way of specific embodiment, the present invention will be further described.
Embodiment 1
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add o-carborane diphenol (2.00g), hexamethylene diamine (0.703g), paraformaldehyde
(0.727g), add 4ml toluene, 2ml ethanol, be to slowly warm up to 80 DEG C, react 5h.Instead
After should terminating, question response product is cooled to room temperature, is instilled the 80ml absolute methanol being stirred continuously
In solution, staticly settling 48h, collect sediment subsequently, 40 DEG C of vacuum drying 3h i.e. can get mesh
Mark product.FTIR,ν(cm-1, KBr compressing tablet): 3422 (-OH stretching vibrations), 2933,2856 (-CH2
Stretching vibration), 2598 (B-H stretching vibrations), 1612,1580,1511 and 1462 (phenyl ring bones
Frame vibrates), 1238,1024 (the asymmetric and symmetrical stretching vibration peaks of C-O-C), 1125 (C-N-C
The asymmetric stretching vibration of key), 934 (piperazine ring skeletal vibrations).1H NMR (400MHz,
CDCl3, ppm), 6.52-7.12 (m, hydrogen in phenyl ring), 4.79 (s, O-CH2-N), 3.83 (s,
Ar-CH2-N), 0.89-3.25 (m, B-H).
Embodiment 2
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add m-carborane diphenol (2.00g), hexamethylene diamine (0.703g), paraformaldehyde
(0.818g), add 4ml toluene, 2ml ethanol, be to slowly warm up to 70 DEG C, react 5h.Instead
After should terminating, question response product is cooled to room temperature, is instilled the 80ml absolute methanol being stirred continuously
In solution, staticly settling 48h, collect sediment subsequently, 40 DEG C of vacuum drying 3h i.e. can get mesh
Mark product.FTIR,ν(cm-1, KBr compressing tablet): 3415 (-OH stretching vibrations), 2916,2846 (-CH2
Stretching vibration), 2599 (B-H stretching vibrations), 1608,1587,1501 and 1461 (phenyl ring bones
Frame vibrates), 1235,1023 (the asymmetric and symmetrical stretching vibration peaks of C-O-C), 1123 (C-N-C
The asymmetric stretching vibration of key), 939 (piperazine ring skeletal vibrations).1H NMR (400MHz,
CDCl3, ppm), 6.50-7.13 (m, hydrogen in phenyl ring), 4.78 (s, O-CH2-N), 3.84 (s,
Ar-CH2-N), 0.89-3.23 (m, B-H).
Embodiment 3
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add p-carborane diphenol (2.00g), hexamethylene diamine (0.703g), paraformaldehyde
(0.727g), add 4ml toluene, 2ml ethanol, be to slowly warm up to 90 DEG C, react 30h.Instead
After should terminating, question response product is cooled to room temperature, is instilled the 80ml absolute methanol being stirred continuously
In solution, staticly settling 24h, collect sediment subsequently, 40 DEG C of vacuum drying 5h i.e. can get mesh
Mark product.FTIR,ν(cm-1, KBr compressing tablet): 3385 (-OH stretching vibrations), 2928,2854 (-CH2
Stretching vibration), 2600 (B-H stretching vibrations), 1611,1585,1509 and 1461 (phenyl ring bones
Frame vibrates), 1239,1022 (the asymmetric and symmetrical stretching vibration peaks of C-O-C), 1126 (C-N-C
The asymmetric stretching vibration of key), 937 (piperazine ring skeletal vibrations).1H NMR (400MHz,
CDCl3, ppm), 6.54-7.13 (m, hydrogen in phenyl ring), 4.80 (s, O-CH2-N), 3.84 (s,
Ar-CH2-N), 0.89-3.26 (m, B-H).
Embodiment 4
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add o-carborane diphenol (2.00g), 4,4-MDA (1.20g),
Paraformaldehyde (0.727g), adds 4ml toluene, 2ml ethanol, is to slowly warm up to 90 DEG C, instead
Answer 5h.After reaction terminates, question response product is cooled to room temperature, is instilled the 80ml being stirred continuously
In absolute methanol solution, staticly settling 40h, collect sediment subsequently, 40 DEG C of vacuum drying 3h are i.e.
Available target product.FTIR,ν(cm-1, KBr compressing tablet): 3026 (unsaturation=c h bonds), 2898
(saturated c h bond), 1612,1582,1505,1422 (phenyl ring skeletal vibrations), 1371,1183
(C-N-C), 1247,1074 (C-O-C), 819,729 (c h bonds in phenyl ring), 973,936
(piperazine ring skeletal vibration), 2588 (B-H keys).1H NMR (400MHz, CDCl3, ppm),
6.52-7.12 (m, hydrogen in phenyl ring), 5.16 (s, O-CH2-N), 4.34 (s, Ar-CH2-N), 1.28-3.25
(m,B-H)。
Embodiment 5
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add m-carborane diphenol (2.00g), 4,4-MDA (1.20g),
Paraformaldehyde (0.727g), adds 4ml toluene, 2ml ethanol, is to slowly warm up to 80 DEG C, instead
Answer 15h.After reaction terminates, question response product is cooled to room temperature, is instilled the 80ml being stirred continuously
In absolute methanol solution, staticly settling 48h, collect sediment subsequently, 40 DEG C of vacuum drying 3h are i.e.
Available target product.FTIR,ν(cm-1, KBr compressing tablet): 3032 (unsaturation=c h bonds), 2896
(saturated c h bond), 1608,1576,1503,1418 (phenyl ring skeletal vibrations), 1374,1186
(C-N-C), 1245,1076 (C-O-C), 818,729 (c h bonds in phenyl ring), 973,935
(piperazine ring skeletal vibration), 2598 (B-H keys).1H NMR (400MHz, CDCl3, ppm),
6.52-7.14 (m, hydrogen in phenyl ring), 5.15 (s, O-CH2-N), 4.36 (s, Ar-CH2-N), 1.25-3.25
(m,B-H)。
Embodiment 6
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add p-carborane diphenol (2.00g), 4,4-MDA (1.20g),
Paraformaldehyde (0.727g), adds 4ml toluene, 2ml ethanol, is to slowly warm up to 80 DEG C, instead
Answer 30h.After reaction terminates, question response product is cooled to room temperature, is instilled the 80ml being stirred continuously
In absolute methanol solution, staticly settling 48h, collect sediment subsequently, 40 DEG C of vacuum drying 3h are i.e.
Available target product.FTIR,ν(cm-1, KBr compressing tablet): 3018 (unsaturation=c h bonds), 2899
(saturated c h bond), 1610,1581,1506,1420 (phenyl ring skeletal vibrations), 1379,1185
(C-N-C), 1245,1076 (C-O-C), 820,729 (c h bonds in phenyl ring), 973,937
(piperazine ring skeletal vibration), 2589 (B-H keys).1H NMR (400MHz, CDCl3, ppm),
6.48-7.11 (m, hydrogen in phenyl ring), 5.18 (s, O-CH2-N), 4.34 (s, Ar-CH2-N), 1.28-3.26
(m,B-H)。
Embodiment 7
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add o-carborane diphenol (2.00g), 4,4-DADPS (1.50g),
Paraformaldehyde (0.727g), adds 4ml toluene, 2ml ethanol, is to slowly warm up to 80 DEG C, instead
Answer 5h.After reaction terminates, question response product is cooled to room temperature, is instilled the 80ml being stirred continuously
In absolute methanol solution, staticly settling 48h, collect sediment subsequently, 40 DEG C of vacuum drying 3h are i.e.
Available target product.FTIR,ν(cm-1, KBr compressing tablet): 3074 (unsaturation=c h bonds), 3007
(saturated c h bond), 1601,1582,1506 (phenyl ring skeletal vibrations), 1371,1183 (C-N-C),
1223,1074 (C-O-C), 1296,1147,1110 (O=S=O), 954 (piperazine ring skeleton
Vibration), 2588 (B-H keys).1H NMR (400MHz, CDCl3, ppm), 6.62-7.33 (m,
Hydrogen in phenyl ring), 5.35 (s, O-CH2-N), 4.63 (s, Ar-CH2-N), 1.28-3.09 (m, B-H).
Embodiment 8
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add m-carborane diphenol (2.00g), 4,4-DADPS (1.50g),
Paraformaldehyde (0.727g), adds 4ml toluene, 2ml ethanol, is to slowly warm up to 80 DEG C, instead
Answer 15h.After reaction terminates, question response product is cooled to room temperature, is instilled the 80ml being stirred continuously
In absolute methanol solution, staticly settling 48h, collect sediment subsequently, 40 DEG C of vacuum drying 3h are i.e.
Available target product.FTIR,ν(cm-1, KBr compressing tablet): 3079 (unsaturation=c h bonds), 2989
(saturated c h bond), 1601,1589,1509 (phenyl ring skeletal vibrations), 1371,1183 (C-N-C),
1223,1074 (C-O-C), 1296,1147,1110 (O=S=O), 957 (piperazine ring skeleton
Vibration), 2595 (B-H keys).1H NMR (400MHz, CDCl3, ppm), 6.59-7.31 (m,
Hydrogen in phenyl ring), 5.36 (s, O-CH2-N), 4.62 (s, Ar-CH2-N), 1.25-3.09 (m, B-H).
Embodiment 9
First the 100mL there-necked flask that will be equipped with magnetic stirring apparatus, thermometer and reflux condensing tube is put
In oil bath pan, add p-carborane diphenol (2.00g), 4,4-DADPS (1.50g),
Paraformaldehyde (0.727g), adds 4ml toluene, 2ml ethanol, is to slowly warm up to 80 DEG C, instead
Answer 30h.After reaction terminates, question response product is cooled to room temperature, is instilled the 80ml being stirred continuously
In absolute methanol solution, staticly settling 48h, collect sediment subsequently, 40 DEG C of vacuum drying 3h are i.e.
Available target product.FTIR,ν(cm-1, KBr compressing tablet): 3058 (unsaturation=c h bonds), 2996
(saturated c h bond), 1611,1578,1505 (phenyl ring skeletal vibrations), 1374,1183 (C-N-C),
1220,1074 (C-O-C), 1296,1147,1110 (O=S=O), 951 (piperazine ring skeleton
Vibration), 2600 (B-H keys).1H NMR (400MHz, CDCl3, ppm), 6.63-7.34 (m,
Hydrogen in phenyl ring), 5.34 (s, O-CH2-N), 4.64 (s, Ar-CH2-N), 1.26-3.12 (m, B-H).
Embodiment 10
2h, thermal weight loss is solidified containing carborane backbone chain type Benzoxazine at 200 DEG C with prepared by embodiment 1
Carbon yield when analyzing lower 900 DEG C of nitrogen atmosphere of display is 80.1%, lower 900 DEG C of oxygen atmosphere residual
Charcoal rate is 89.5%.
Embodiment 11
At 200 DEG C, 2h is solidified, containing heat by the backbone chain type Benzoxazine containing carborane of embodiment 2 preparation
Carbon yield during zero-g aircraft lower 900 DEG C of nitrogen atmosphere of display is 79.8%, lower 900 DEG C of oxygen atmosphere
Carbon yield be 88.6%.
Embodiment 12
Solidifying 2h at 200 DEG C by the backbone chain type Benzoxazine containing carborane of embodiment 3 preparation, heat is lost
Carbon yield during weight analysis lower 900 DEG C of nitrogen atmosphere of display is 78.7%, lower 900 DEG C of oxygen atmosphere
Carbon yield is 87.5%.
Embodiment 13
Solidifying 2h at 260 DEG C by the backbone chain type Benzoxazine containing carborane of embodiment 4 preparation, heat is lost
Carbon yield during weight analysis lower 900 DEG C of nitrogen atmosphere of display is 83.3%, lower 900 DEG C of oxygen atmosphere
Carbon yield is 89.9%.
Embodiment 14
Solidifying 2h at 260 DEG C by the backbone chain type Benzoxazine containing carborane of embodiment 5 preparation, heat is lost
Carbon yield during weight analysis lower 900 DEG C of nitrogen atmosphere of display is 82.6%, lower 900 DEG C of oxygen atmosphere
Carbon yield is 88.3%.
Embodiment 15
Solidifying 2h at 260 DEG C by the backbone chain type Benzoxazine containing carborane of embodiment 6 preparation, heat is lost
Carbon yield during weight analysis lower 900 DEG C of nitrogen atmosphere of display is 82.3%, lower 900 DEG C of oxygen atmosphere
Carbon yield is 87.9%.
Embodiment 16
Solidifying 2h at 280 DEG C by the backbone chain type Benzoxazine containing carborane of embodiment 7 preparation, heat is lost
Carbon yield during weight analysis lower 900 DEG C of nitrogen atmosphere of display is 85.3%, lower 900 DEG C of oxygen atmosphere
Carbon yield is 90.0%.
Embodiment 17
Solidifying 2h at 280 DEG C by the backbone chain type Benzoxazine containing carborane of embodiment 8 preparation, heat is lost
Carbon yield during weight analysis lower 900 DEG C of nitrogen atmosphere of display is 84.6%, lower 900 DEG C of oxygen atmosphere
Carbon yield is 88.6%.
Embodiment 18
Solidifying 2h at 280 DEG C by the backbone chain type Benzoxazine containing carborane of embodiment 9 preparation, heat is lost
Carbon yield during weight analysis lower 900 DEG C of nitrogen atmosphere of display is 83.8%, lower 900 DEG C of oxygen atmosphere
Carbon yield is 86.9%.
In sum, the synthesis related in the present invention and curing, process is simple, it is not necessary to
Harsh pollution control measures.After solidifying containing carborane backbone chain type Benzoxazine, solidfied material is at nitrogen gas
Carbon yield after the lower 900 DEG C of ablations of atmosphere is up to 80-90%, is the desirable feedstock of high temperature resistant composite.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, to ordinary skill
For personnel, can be improved according to the above description or convert, all these modifications and variations are all answered
Belong to the protection domain of claims of the present invention.
Claims (7)
1. the synthetic method containing carborane backbone chain type Benzoxazine, it is characterised in that include following
Step:
Carborane diphenol, paraformaldehyde, diamines, solvent are added in reaction system, is warming up to 70-90
DEG C, reaction 5-30h obtains containing carborane backbone chain type Benzoxazine；
Wherein, solvent is the mixed liquor of toluene and ethanol.
Synthetic method containing carborane backbone chain type Benzoxazine the most according to claim 1, it is special
Levying and be, carborane diphenol is m-carborane bis-phenol, p-carborane bis-phenol or o-carborane bis-phenol.
Synthetic method containing carborane backbone chain type Benzoxazine the most according to claim 1, it is special
Levy and be, diamines be hexamethylene diamine, 4,4-MDA or 4,4-DADPS.
Synthetic method containing carborane backbone chain type Benzoxazine the most according to claim 1, it is special
Levying and be, the volume ratio of toluene and ethanol is (2-3): 1.
5. according to the arbitrary described synthetic method containing carborane backbone chain type Benzoxazine of Claims 1 to 4,
It is characterized in that, carborane diphenol, paraformaldehyde, the mol ratio of diamines are 1:(4-4.5): 1.
Synthetic method containing carborane backbone chain type Benzoxazine the most according to claim 1, it is special
Levy and be, further comprising the steps of:
To instill in the absolute methanol solution being stirred continuously containing carborane backbone chain type Benzoxazine, it is heavy to stand
Shallow lake 24-48h；
Suction filtration, collects sediment, 40 DEG C of vacuum drying 3-5h.
7. the curing containing carborane backbone chain type Benzoxazine, it is characterised in that described carbon containing
Method as described in the employing of borine backbone chain type Benzoxazine is as arbitrary in claim 1～6 prepares, and it is solid
Change method comprises the following steps:
Solidification 2-4h at carborane backbone chain type Benzoxazine is placed in 180-260 DEG C will be contained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610327062.2A CN105837818B (en) | 2016-05-17 | 2016-05-17 | Synthesis and curing method of carborane-containing main chain type benzoxazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610327062.2A CN105837818B (en) | 2016-05-17 | 2016-05-17 | Synthesis and curing method of carborane-containing main chain type benzoxazine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105837818A true CN105837818A (en) | 2016-08-10 |
| CN105837818B CN105837818B (en) | 2020-10-02 |
Family
ID=56592618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610327062.2A Active CN105837818B (en) | 2016-05-17 | 2016-05-17 | Synthesis and curing method of carborane-containing main chain type benzoxazine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105837818B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283194A (en) * | 2019-07-31 | 2019-09-27 | 郑州原理生物科技有限公司 | The preparation method of the double hydroxyl substitutive derivatives of carborane between 1,7- |
| CN114395095A (en) * | 2022-01-24 | 2022-04-26 | 衡阳师范学院 | Method for synthesizing main chain type benzoxazine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516537A (en) * | 2011-12-09 | 2012-06-27 | 浙江大学宁波理工学院 | Aromatic diamine type cyano group-containing benzoxazine resin and its preparation method |
| CN104327105A (en) * | 2014-09-22 | 2015-02-04 | 北京化工大学 | Synthesis and curing method of carborane benzo oxazine resin |
-
2016
- 2016-05-17 CN CN201610327062.2A patent/CN105837818B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516537A (en) * | 2011-12-09 | 2012-06-27 | 浙江大学宁波理工学院 | Aromatic diamine type cyano group-containing benzoxazine resin and its preparation method |
| CN104327105A (en) * | 2014-09-22 | 2015-02-04 | 北京化工大学 | Synthesis and curing method of carborane benzo oxazine resin |
Non-Patent Citations (1)
| Title |
|---|
| SHICHENG QI ET AL.: ""Synthesis, characterization, and curing behavior of carborane-containing benzoxazine resins with excellent thermal and thermo-oxidative stability"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283194A (en) * | 2019-07-31 | 2019-09-27 | 郑州原理生物科技有限公司 | The preparation method of the double hydroxyl substitutive derivatives of carborane between 1,7- |
| CN110283194B (en) * | 2019-07-31 | 2021-11-16 | 郑州原理生物科技有限公司 | Preparation method of 1, 7-m-carborane dihydroxyl substituted derivative |
| CN114395095A (en) * | 2022-01-24 | 2022-04-26 | 衡阳师范学院 | Method for synthesizing main chain type benzoxazine |
| CN114395095B (en) * | 2022-01-24 | 2023-12-19 | 衡阳师范学院 | Synthesis method of main chain type benzoxazine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105837818B (en) | 2020-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107629082B (en) | A kind of novel siliceous benzoxazine and preparation method thereof | |
| CN106519226B (en) | Polytriazoles resin derived from a kind of trifunctional alkynes and preparation method thereof | |
| Zhang et al. | Sustainable glucose-based phenolic resin and its curing with a DGEBA epoxy resin | |
| Xiong et al. | Alkynyl-functionalized benzoxazine containing phthalide side group: Synthesis, characterization and curing mechanism | |
| Zhang et al. | A Visible‐Light‐Induced Strategy To Construct Osmanaphthalynes, Osmaanthracyne, and Osmaphenanthryne | |
| CN110591091A (en) | Main chain type benzoxazine containing daidzein group and preparation method thereof | |
| CN105837818A (en) | Synthesizing and curing methods for main-chain benzoxazine containing carborane | |
| CN107522831B (en) | A kind of siliceous benzoxazine of high-temperature resistant low dielectric and preparation method thereof | |
| Li et al. | Synthesis, characterization of new bisphenol-based benzoxazines and the thermal properties of their polymers | |
| Chen et al. | New epoxy resins. I. The stability of epoxy–trialkoxyboroxines triaryloxyboroxine system | |
| Chen et al. | Synthesis and characterization of a novel siloxane‐imide‐containing polybenzoxazine | |
| Xu et al. | Synthesis and characterization of organic–inorganic hybrid polymers with a well‐defined structure from diamines and epoxy‐functionalized polyhedral oligomeric silsesquioxanes | |
| Sha et al. | Large free volume biobased benzoxazine resin: Synthesis and characterization, dielectric properties, thermal and mechanical properties | |
| CN104327105B (en) | The synthesis of carborane benzoxazine resins and curing | |
| Gao et al. | Octa (aminophenyl) polyhedral oligomeric silsesquioxane/boron‐containing phenol–formaldehyde resin nanocomposites: Synthesis, cured, and thermal properties | |
| Fan et al. | Synthesis, characterization, and thermal curing of a novel polyhedral oligomeric octa (propargylaminophenyl) silsesquioxane | |
| Huang et al. | Star‐shaped silicon‐containing arylacetylene resin based on a one‐pot synthesis using zinc powder catalysis with improved processing and thermal properties | |
| Zhang et al. | Design of new benzoxazines with excellent thermal stability and processability using the “gold panning” method | |
| Habets et al. | Facile Access to CO2‐Sourced Polythiocarbonate Dynamic Networks And Their Potential As Solid‐State Electrolytes For Lithium Metal Batteries | |
| Liu et al. | Synthesis of a novel series of propargyloxyphenyl maleimides and their characterization as thermal‐resistance resins | |
| Kumar et al. | Synthesis and characterization of novel cyclotriphosphazene-containing poly (ether imide) s | |
| CN113429363B (en) | Benzoxazine and synthetic method thereof | |
| Li et al. | Synthesis and properties of poly (silylene bis (ethynylphenoxy) diphenylsulfone) | |
| Li et al. | Synthesis, characterization, and properties of a polyhedral oligomeric octadiphenylsulfonylsilsesquioxane | |
| CN102321246B (en) | Polyborazine ceramic precursor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |