CN103524746A - Borazine aryne resin and preparation method thereof - Google Patents
Borazine aryne resin and preparation method thereof Download PDFInfo
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- CN103524746A CN103524746A CN201310487472.XA CN201310487472A CN103524746A CN 103524746 A CN103524746 A CN 103524746A CN 201310487472 A CN201310487472 A CN 201310487472A CN 103524746 A CN103524746 A CN 103524746A
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Abstract
The invention discloses a borazine aryne resin and a preparation method thereof. The borazine aryne resin is structurally characterized in that the polymer molecular chain contains borazine and aryl alkynyl structures. The preparation method of the resin comprises the following steps: on the basis of taking diacetylene-benzene, boron trihalide and ammonium chloride or organic primary amine as raw materials, reacting in three steps in the presence of an inert gas so as to synthesize the borazine aryne resin. The preparation method is simple in process, convenient to operate and short in reaction time, the process condition is easy to control, and the aftertreatment process is simple; the borazine aryne resin is reddish brown viscous fluid or faint yellow solid, and can be solidified in a light and thermal polymerization mode; the borazine aryne resin has excellent thermal resistance and low dielectric property, can be used for preparing an advanced resin-based composite material, can be also used as a low dielectric material, and can be widely applied to the fields of aerospace and electronic information.
Description
Technical field
The present invention relates to features macromolecular material, specifically, is a kind of borazine aryne resin and preparation method thereof.
Background technology
Along with the development of information technology, the characteristic dimension of super large-scale integration (ULSI) is constantly being dwindled by Moore's Law, and the demand of advanced low-k materials is subject to people's attention; In addition, the fast development of aeronautical and space technology, has higher requirement to the performance of high temperature resistant wave-permeable material.And the dielectric properties of traditional organic resin and resistance to elevated temperatures can not meet the demand of hypersonic vehicle, super large-scale integration and chip.
Poly-aryl ethane resin has good building-up properties, good dielectric properties and excellent resistance to elevated temperatures, and poly-aryl ethane resin is applied at aerospace field as high temperature resistant wave-permeable material.Borazine has stable structure, containing the compound of borazine ring skeleton, has low molecular polarizability and low specific inductivity.G.R.Dennis simulates borazine (B by molecular orbital method
3n
3h
6) specific inductivity be 1.9, and the specific inductivity of phenyl ring is 2.2, research shows to have high thermostability and low specific inductivity containing the compound of borazine.The people such as Hiroshi Matsutani utilize ethynyl borazine and hydrogen-containing siloxane to carry out addition reaction of silicon with hydrogen, the material of having prepared low-k is applied to super unicircuit, has effectively reduced signal delay and the power loss of super large-scale integration (ULSI).
The present invention is incorporated into borazine skeleton in poly-aryl ethane resin structure, preparation is containing the borazine aryne resin of borazine and sweet-smelling alkynyl, under the effect of heat and catalyzer, pass through carbon carbon triple bond generation crosslinking curing, the poly-aromatic ring structure of borazine hydridization that height of formation is crosslinked, give specific inductivity and superior heat resistance performance that material is very low, to meet the demand of the field development of aerospace and electronic information.
Summary of the invention
One of object of the present invention is to provide a kind of borazine aryne resin with high-temperature resistant low dielectric constant.
Two of object of the present invention is to provide the preparation method of described borazine aryne resin, reacts the described borazine aryne resin of preparation by sweet-smelling alkynyl Grignard reagent with three halogen borazine condensation polymerizations.
Technical scheme of the present invention is specific as follows:
An aryne resin, described borazine aryne resin has following structural formula:
Wherein, R is H, CH
3, CH
3cH
2, CH
2=CHCH
2, C
6h
5; Polymerization degree n=1～20.
The preparation method of above-mentioned borazine aryne resin, comprises and is prepared as follows step:
(1) ammonium chloride or organic primary amine are mixed with boron trihalides in solvent, be then heated to 100～150 ℃ of temperature of reaction, in 2～20 hours reaction times, generate three halogen borazines.Preferably, temperature of reaction is 110～130 ℃ of C, and the reaction times is 5～12 hours;
(2) under inert gas protection, in anhydrous solvent, halohydrocarbon is reacted with magnesium powder and generate alkyl Grignard reagent, then react with diacetylene-benzene and generate sweet-smelling alkynyl Grignard reagent;
(3) the sweet-smelling alkynyl Grignard reagent of step (2) is added in three halogen borazines of step (1), at-20～30 ℃, polyreaction is 0.5～6 hour, then carries out aftertreatment, obtains described borazine aryne resin.Temperature of reaction is preferably 0～20 ℃, and the reaction times is preferably 2～4 hours.
Solvent described in step (1) is one or more the mixture in benzene, toluene, chlorobenzene.Be preferably the mixed solvent of toluene or toluene and chlorobenzene.
Described in step (1), boron trihalides is boron trichloride or boron tribromide.
The alkyl or aryl halides that described in step (2), halohydrocarbon is C2～C12.
Anhydrous solvent described in step (2) is one or more the mixture in tetrahydrofuran (THF), toluene, ether and dioxane, is preferably the mixed solvent of tetrahydrofuran (THF) or tetrahydrofuran (THF) and toluene.
The preparation process reaction formula of described borazine aryne resin is given an example schematically as follows:
1) boron trihalides reacts with ammonium chloride or organic primary amine:
Wherein, R=H or R ';
2) Grignard reagent reacts with diacetylene-benzene:
R'Br+Mg→R'MgBr
3) three halogen borazines react with diacetylene-benzene Grignard reagent:
Borazine aryne resin of the present invention contains borazine and aryne group in molecular structure, under heat, light or catalyst action, can pass through sweet-smelling alkynyl crosslinking curing, height of formation is crosslinked, the hybrid inorganic-organic materials of high aromatic ring structure, give resin good resistance toheat, the introducing of borazine is given again resin and is had low-k and low-dielectric loss.
Accompanying drawing explanation
Fig. 1 is the infrared spectra of the triallyl trichlorine borazine (TV-TCB) of embodiment 2;
Fig. 2 is the infrared spectra (FTIR) of the borazine aryne polymkeric substance (PBZA-1) of embodiment 3;
Fig. 3 is the DSC figure of the borazine aryne polymkeric substance (PBZA-1) of embodiment 3;
Fig. 4 is TGA figure in the nitrogen of borazine aryne polymkeric substance (PBZA-1) of embodiment 3;
Fig. 5 is that the specific inductivity of borazine aryne polymkeric substance (PBZA-1) of embodiment 3 and dielectric loss are with frequency variation curve figure.
Fig. 6 be embodiment 4 containing the specific inductivity of allyl group borazine aryne polymkeric substance (PBZA-2) and dielectric loss with frequency variation curve figure.
Embodiment
By the following examples borazine aryne resin of the present invention and preparation method thereof is specifically described, but embodiment is only for the present invention is further described, does not limit the scope of the invention.
Synthesizing of embodiment 1 trichlorine borazine (TCB)
In being furnished with the 500ml four-hole boiling flask of nitrogen conduit, agitator, thermometer and prolong, through vacuumizing, leading to after nitrogen circulating dehumidification deoxygenation several times, add NH
4cl powder 32g (0.30mol) and toluene 300ml, and vigorous stirring formation suspension liquid, be heated to after 110 ℃, in four-hole boiling flask, passes into slowly BCl
3gas, at this temperature, insulation reaction 10h, is cooled to room temperature.Then adopt shleck technology suction filtration under nitrogen protection, filtrate transferring to revolved and steamed in bottle, and underpressure distillation removes desolventizing and obtains colourless acicular crystal trichlorine borazine (TCB), and infrared spectra as shown in Figure 1.
Synthesizing of embodiment 2 triallyl trichlorine borazines (TV-TCB)
In being furnished with the 500ml four-hole boiling flask of nitrogen conduit, agitator, thermometer and prolong, through vacuumizing, leading to after nitrogen circulating dehumidification deoxygenation several times, add BCl
3(0.09mol) toluene solution, with salt ice, be cooled to-10 ℃ and slowly drip wherein triethylamine 18.22g(0.18mol) and the mixed solution of toluene (20mL), after dropwising, in system, add allyl amine 5.14g(0.09mol again) and toluene (10mL), afterwards system is slowly risen to 110 ℃ of insulation 6h, be cooled to room temperature.Adopt shleck technology suction filtration under nitrogen protection, filtrate transferring to revolved and steamed in bottle, and underpressure distillation removes desolventizing and obtains colourless transparent liquid triallyl trichlorine borazine (TV-TCB), and infrared spectra as shown in Figure 1.
Synthesizing of embodiment 3 borazine aryne resins (PBZA-1)
(1), in being furnished with the 500ml four-hole boiling flask of nitrogen conduit, agitator, thermometer and prolong, through vacuumizing, leading to after nitrogen circulating dehumidification deoxygenation several times, add NH
4cl powder 32g (0.30mol) and toluene 300ml, and vigorous stirring formation suspension liquid, be heated to after 110 ℃, in four-hole boiling flask, passes into slowly BCl
3gas, at this temperature, insulation reaction 10h, is cooled to room temperature.Then adopt shleck technology suction filtration under nitrogen protection, filtrate transferring to revolved and steamed in bottle, and underpressure distillation removes desolventizing and obtains colourless acicular crystal trichlorine borazine (TCB).
(2) under nitrogen protection; magnesium powder 3.20g (0.13mol)/tetrahydrofuran (THF) (80ml) is joined in 500ml four-hole boiling flask; cooling with cooling bath; by constant pressure funnel, drip wherein the mixed solution that adds monobromethane (EtBr) 13.08g (0.12mol) and tetrahydrofuran (THF) (30ml); then be heated to 50 ℃ of reactions after 2 hours; be cooled to room temperature; then by constant pressure funnel to the mixed solution that drips diacetylene-benzene 15.12g (0.12mol)/tetrahydrofuran (THF) (30ml) in system; be heated to 70 ℃ of reactions 2 hours, obtain diacetylene-benzene grignard reagent solution.
(3) diacetylene-benzene grignard reagent solution step (2) being obtained is bathed and is cooled to-8 ℃ with cryosel, adds trichlorine borazine (TCB) 7.36g (0.02mol)/toluene (30mL), and is heated to 30 ℃ of insulation reaction 4 hours.Then add dioxane, continue to stir 1 hour, remove by filter precipitation, filtrate is removed desolventizing with the distillation of rotary distillation device and is obtained borazine aryne resin PBZA-1.
As shown in Figure 2, FTIR:3430cm
-1for the absorption peak of N-H, 3290cm
-1for the absorption peak of ≡ C-H, 2180cm
-1the stretching vibration peak of Wei – Ph-C ≡ CH, 1459cm
-1absorption peak for BN key.
PBZA-1's
1h-NMR (CDCl
3): 3.04ppm is the chemical shift of Terminal Acetylenes hydrogen, and 7.1～7.6ppm is the chemical shift of phenyl ring hydrogen.
Borazine aryne resin PBZA-1 dissolves in tetrahydrofuran (THF), dimethyl formamide, toluene and chloroform equal solvent.
As shown in Figure 3, be the differential scanning calorimetric curve (DSC) of borazine aryne resin PBZA-1, after borazine aryne resin solidifies under 120 ℃/2h+180 ℃/2h+210 ℃/4h+250 ℃/2h condition, obtain the black solid of fine and close light.
As shown in Figure 4, be thermogravimetic analysis (TGA) (TGA) curve of borazine aryne resin PBZA-1 cured article in nitrogen.Thermal weight loss 5% temperature (T in nitrogen atmosphere
d5) be 376 ℃, 1000 ℃ of residual rates are 79.7%.
As shown in Figure 5, the specific inductivity of borazine aryne resin PBZA-1 cured article and dielectric loss are with the change curve of frequency, and when frequency is power frequency 60Hz, specific inductivity is 2.79, and dielectric loss is 1.4 * 10
-3; Specific inductivity when frequency is 1MHz is 2.77, and dielectric loss is 2.8 * 10
-3.
Synthesizing of embodiment 4 borazine aryne resins (PBZA-2)
(1), in being furnished with the 500ml four-hole boiling flask of nitrogen conduit, agitator, thermometer and prolong, through vacuumizing, leading to after nitrogen circulating dehumidification deoxygenation several times, add BCl
3(0.09mol) toluene solution, with salt ice, be cooled to-10 ℃ and slowly drip wherein triethylamine 18.22g(0.18mol) and the mixed solution of toluene (20mL), after dropwising, in system, add allyl amine 5.14g(0.09mol again) and toluene (10mL), afterwards system is slowly risen to 110 ℃ of insulation 6h, be cooled to room temperature.Adopt shleck technology suction filtration under nitrogen protection, filtrate transferring to revolved and steamed in bottle, and underpressure distillation removes desolventizing and obtains colourless transparent liquid triallyl trichlorine borazine (TV-TCB).
(2) under nitrogen protection; by magnesium powder 3.20g(0.13mol)/THF (80ml) is placed in 500mL four-hole boiling flask; cooling with cooling bath; and add wherein monobromethane (EtBr) 13.08g(0.12mol)/THF(30mL); then 50 ℃ of reactions are after 2 hours; in cooled system, drip diacetylene-benzene 15.12g(0.12mol)/THF(20mL), and at 70 ℃, react 2 hours.
(3) with cryosel, bathe and system is cooled to-8 ℃, and add wherein triallyl trichlorine borazine (TVCB) 12.16g (0.04mol)/toluene (30mL), and be incubated 4 hours at 30 ℃.The salt that adds dioxane precipitation to generate, removes by filter precipitation, and filtrate is distilled away toluene with rotary distillation device and obtained encircling boron aryne resin PBZA-2.
PBZA-2:FTIR:3290cm
-1for the absorption peak of ≡ C-H, 2180cm
-1the stretching vibration peak 1429cm of Wei – ph-≡ CH
-1for the absorption peak of BN key, 1641cm
-1for-CH=CH
2absorption peak;
PBZA-2:
1h-NMR (CDCl
3): 3.04ppm is the chemical shift of Terminal Acetylenes hydrogen, and 7.10～7.60ppm is the chemical shift of phenyl ring hydrogen, and 6.02～5.86ppm is-C
h 2-Hydrochemistry displacement, 4.42ppm is-C
h=CH
2hydrochemistry displacement, 4.93～5.26ppm is-CH=C
h 2hydrochemistry displacement.
Borazine aryne resin PBZA-2 dissolves in tetrahydrofuran (THF), dimethyl formamide, toluene and chloroform equal solvent.After resin solidifies under 120 ℃/2h+180 ℃/2h+210 ℃/4h+250 ℃/2h condition, obtain the black solid of fine and close light.
Borazine aryne resin PBZA-2 cured article residual rate in 1000 ℃ of nitrogen environments is 75.3%.Borazine aryne resin PBZA-2 cured article has excellent dielectric properties.Its cured article specific inductivity and dielectric loss are shown in Fig. 6 with the change curve of frequency, and when frequency is power frequency 60Hz, specific inductivity is 2.74, and dielectric loss is 1.8 * 10
-3; Frequency is 1 * 10
5specific inductivity during Hz is 2.72, and dielectric loss is 1.7 * 10
-3.
Claims (8)
1. a borazine aryne resin, is characterized in that, described borazine aryne resin has following structural formula:
Wherein, R is H, CH
3, CH
3cH
2, CH
2=CHCH
2, C
6h
5; Polymerization degree n=1～20.
2. the preparation method of borazine aryne resin described in claim 1, is characterized in that, comprises and is prepared as follows step:
(1) ammonium chloride or organic primary amine are mixed with boron trihalides in solvent, then at 100～150 ℃, react 2～20 hours, generate three halogen borazines;
(2) under inert gas protection, in anhydrous solvent, halohydrocarbon is reacted with magnesium powder and generate alkyl Grignard reagent, then react with diacetylene-benzene and generate sweet-smelling alkynyl Grignard reagent;
(3) the sweet-smelling alkynyl Grignard reagent of step (2) is added in three halogen borazines of step (1), at-20～30 ℃, polyreaction is 0.5～6 hour, obtains described borazine aryne resin.
3. preparation method according to claim 2, is characterized in that, described in step (1), organic primary amine is CH
3nH
2, CH
3cH
2nH
2, CH
2=CHCH
2nH
2or C
6h
5nH
2.
4. preparation method according to claim 2, is characterized in that, solvent described in step (1) is one or more the mixture in benzene, toluene, chlorobenzene.
5. preparation method according to claim 2, is characterized in that, described in step (1), boron trihalides is boron trichloride or boron tribromide.
6. preparation method according to claim 2, is characterized in that, the temperature of reaction of step (1) is 110～130 ℃, and the reaction times is 5～12 hours.
7. preparation method according to claim 2, is characterized in that, the alkyl or aryl halides that described in step (2), halohydrocarbon is C2～C12.
8. preparation method according to claim 2, is characterized in that, anhydrous solvent described in step (2) is one or more the mixture in tetrahydrofuran (THF), toluene, ether and dioxane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707234A (en) * | 2018-04-26 | 2018-10-26 | 华东理工大学 | A kind of silicon boron azane ceramic forerunner polymer containing borazine, preparation method and applications |
| CN109180713A (en) * | 2018-08-10 | 2019-01-11 | 华东理工大学 | A kind of diine amino halogenation boron, boracic nitrogen aryne resin and preparation method |
| CN111454396A (en) * | 2020-05-25 | 2020-07-28 | 福建华夏蓝新材料科技有限公司 | Weather-resistant polyacrylate emulsion and preparation method thereof |
| CN112375094A (en) * | 2020-11-25 | 2021-02-19 | 中国人民解放军国防科技大学 | Catalyst-free high-yield synthesis method and device for trichloroborazine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101310038A (en) * | 2005-11-17 | 2008-11-19 | 株式会社日本触媒 | Composition for chemical vapor deposition film-formation and method for production of low dielectric constant film |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101310038A (en) * | 2005-11-17 | 2008-11-19 | 株式会社日本触媒 | Composition for chemical vapor deposition film-formation and method for production of low dielectric constant film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707234A (en) * | 2018-04-26 | 2018-10-26 | 华东理工大学 | A kind of silicon boron azane ceramic forerunner polymer containing borazine, preparation method and applications |
| CN109180713A (en) * | 2018-08-10 | 2019-01-11 | 华东理工大学 | A kind of diine amino halogenation boron, boracic nitrogen aryne resin and preparation method |
| CN109180713B (en) * | 2018-08-10 | 2020-08-28 | 华东理工大学 | Diacetylene amino boron halide, boron-nitrogen-containing aryne resin and preparation method thereof |
| CN111454396A (en) * | 2020-05-25 | 2020-07-28 | 福建华夏蓝新材料科技有限公司 | Weather-resistant polyacrylate emulsion and preparation method thereof |
| CN111454396B (en) * | 2020-05-25 | 2021-10-08 | 福建华夏蓝新材料科技有限公司 | Weather-resistant polyacrylate emulsion and preparation method thereof |
| CN112375094A (en) * | 2020-11-25 | 2021-02-19 | 中国人民解放军国防科技大学 | Catalyst-free high-yield synthesis method and device for trichloroborazine |
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