CN106397085B - The synthetic method of 4- vinyl benzocyclobutene - Google Patents
The synthetic method of 4- vinyl benzocyclobutene Download PDFInfo
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Abstract
The invention discloses a kind of synthetic methods of 4- vinyl benzocyclobutene, the following steps are included: being added 4- bromine benzocyclobutene and catalyst dissolved in the solvent of acid binding agent, and it is in nitrogen atmosphere, then pass to ethylene gas, reaction pressure is set to reach 1~10MPa, it seals and heats up and be stirred to react, obtain reaction solution, 4- vinyl benzocyclobutene is obtained after reaction solution is handled.The present invention is using 4- bromine benzocyclobutene as raw material, single step reaction in autoclave, obtains target product 4- vinyl benzocyclobutene, this programme is low in cost, simple process, easy to operate.
Description
Technical field
The present invention relates to a kind of synthetic methods of 4- vinyl benzocyclobutene, especially by 4- bromine benzocyclobutene and second
The method of alkene gas single step reaction synthesis 4- vinyl benzocyclobutene.
Background technique
Benzocyclobutane alkenes compound is a kind of compound with high reaction activity, by the copolymerization of different monomers, altogether
It is the methods of mixed that it is modified, various high performance resin materials can be synthesized.Benzocyclobutane vinyl resin is that one kind has
The novel high polymer material of excellent high temperature resistance, dielectric properties and hydrophobicity performance.It can be gone back on a printed-wiring board
It can be used as integrated circuit interlayer insulating materials.There is an urgent need to novel polymerics for miniaturization, high speed and the densification of microelectronic element
Object dielectric material, and require to be easily worked, good smooth behavior, low-k and good mechanical performance.Benzo ring
Butylene has low hygroscopicity and excellent stress behavior and good metal adhesion (including bonding with copper, gold, aluminium), owns
Benzocyclobutane vinyl resin can meet these requirements.In addition, also having largely in terms of composite material with fields such as bio-medicals
Using.Therefore, benzocyclobutane alkenes compound all had either in terms of the synthesis or in terms of in engineer application it is wide before
Scape.With carrying out in a deep going way for research and development, application will be more and more extensive.Wherein, 4- vinyl benzocyclobutene is exactly benzene
And one of important monomer material of ring class D olefine resin, it is led in insulation, composite material, bio-medical and encapsulating material etc.
There is a preferable application in domain, but its synthetic method is main as shown in Figure 1, be multistep reaction at present, and synthetic method need it is severe
The condition of ultralow temperature at quarter, operation is more many and diverse, and comprehensive yield is low.
Summary of the invention
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later
Point.
In order to realize these purposes and other advantages according to the present invention, a kind of 4- vinyl benzocyclobutene is provided
Synthetic method, comprising the following steps: 4- bromine benzocyclobutene and catalyst are added dissolved in the solvent of acid binding agent, and make at its
In nitrogen atmosphere, ethylene gas is then passed to, reaction pressure is made to reach 1~10MPa, seals and heats up and be stirred to react, is obtained
Reaction solution obtains 4- vinyl benzocyclobutene after handling reaction solution.
Preferably, the weight ratio of the 4- bromine benzocyclobutene and acid binding agent is 1~3:1.
Preferably, the weight ratio of the 4- bromine benzocyclobutene and solvent is 1:1.5~3.
Preferably, the solvent is the deionized water and organic solvent that weight ratio is 1:1.
Preferably, the organic solvent is n,N-Dimethylformamide, acetonitrile, tetrahydrofuran, toluene, methanol and Isosorbide-5-Nitrae-
Any one in dioxane.
Preferably, the solvent dissolved with acid binding agent the preparation method comprises the following steps: by acid binding agent, deionized water and organic solvent
It is mixed, is warming up to 50~60 DEG C, dissolution obtains solvent completely.
Preferably, the acid binding agent is any one in potassium carbonate, potassium acetate and sodium acetate.
Preferably, the catalyst is the palladium acetate and triphenylphosphine that molar ratio is 1:2~4；The palladium acetate adds
Enter 2~5 ‰ that amount is 4- bromine benzocyclobutene molal quantity；The additional amount of the triphenylphosphine is 4- bromine benzocyclobutene molal quantity
4~10 ‰.
Preferably, the temperature of the heating is 70~90 DEG C；The time being stirred to react is 5~8 hours；Be stirred to react to
Pressure stops heating after dropping to 0.5~4MPa.
Preferably, the process of the reaction solution processing are as follows: by reaction solution split-phase, obtain oily phase and water phase；Water phase second
Ether extraction, obtained ether phase mutually merge with oil, are then cleaned respectively with deionized water and saturated sodium chloride solution, anhydrous slufuric acid
Sodium is dry, and solvent is evaporated off in dry back spin, is condensed into pale yellow oily liquid, carries out vacuum distillation using high vacuum oil pump and mentions
It is pure, 75~80 DEG C of fraction is collected, colourless transparent oil liquid 4- vinyl benzocyclobutene is obtained.
The present invention is include at least the following beneficial effects: using 4- bromine benzocyclobutene as raw material, single step reaction in autoclave is obtained
To target product 4- vinyl benzocyclobutene, this programme is low in cost, simple process, easy to operate.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention:
Fig. 1 is the chemical equation of 4- vinyl benzocyclobutene preparation in the prior art.
Fig. 2 is the chemical equation of 4- vinyl benzocyclobutene preparation in the present invention.
Specific embodiment:
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
Embodiment 1:
A kind of synthetic method of 4- vinyl benzocyclobutene, comprising the following steps: be added in autoclave dissolved with carbonic acid
Then the solvent of potassium 4- bromine benzocyclobutene and catalyst is added in solvent, close kettle cover；Using in nitrogen displacement autoclave
Air three times, then passes to ethylene gas, and reaction pressure is made to reach 1MPa, seals and is warming up to 70 DEG C, is stirred to react 5 hours,
Pressure drops to 0.5MPa, stops heating, obtains reaction solution, by reaction solution split-phase, obtains oily phase and water phase；Water phase is extracted with ether
It takes 2 times, obtained ether phase mutually merges with oil, is then cleaned 1 time with deionized water and saturated sodium chloride solution respectively, anhydrous sulphur
Sour sodium drying 4 hours or more, solvent was evaporated off in dry back spin, is condensed into pale yellow oily liquid, is carried out using high vacuum oil pump
Vacuum distillation purification, collects 75~80 DEG C of fraction, obtains colourless transparent oil liquid 4- vinyl benzocyclobutene, purity
Greater than 97%, yield 75%；The weight ratio of the 4- bromine benzocyclobutene and potassium carbonate is 1:1；The 4- bromine benzocyclobutane
The weight ratio of alkene and solvent is 1:1.5；The solvent is the deionized water and organic solvent that weight ratio is 1:1；It is described organic molten
Agent is n,N-Dimethylformamide；The additional amount of the palladium acetate is the 2 ‰ of 4- bromine benzocyclobutene molal quantity；The triphenyl
The additional amount of phosphine is the 4 ‰ of 4- bromine benzocyclobutene molal quantity.
Embodiment 2:
A kind of synthetic method of 4- vinyl benzocyclobutene, comprising the following steps: be added in autoclave dissolved with carbonic acid
Then the solvent of potassium 4- bromine benzocyclobutene and catalyst is added in solvent, close kettle cover；Using in nitrogen displacement autoclave
Air three times, then passes to ethylene gas, and reaction pressure is made to reach 10MPa, seals and is warming up to 90 DEG C, is stirred to react 8 hours,
Pressure drops to 3MPa, stops heating, obtains reaction solution, by reaction solution split-phase, obtains oily phase and water phase；Water phase is extracted with ether
2 times, obtained ether phase mutually merges with oil, then cleans 1 time with deionized water and saturated sodium chloride solution respectively, anhydrous slufuric acid
Sodium drying 4 hours or more, solvent was evaporated off in dry back spin, is condensed into pale yellow oily liquid, is subtracted using high vacuum oil pump
Distilation is pressed, 75~80 DEG C of fraction is collected, obtains colourless transparent oil liquid 4- vinyl benzocyclobutene, purity is big
In 97%, yield 75.2%；The weight ratio of the 4- bromine benzocyclobutene and potassium carbonate is 3:1；The 4- bromine benzocyclobutane
The weight ratio of alkene and solvent is 1:3；The solvent is the deionized water and organic solvent that weight ratio is 1:1；The organic solvent
For n,N-Dimethylformamide；The additional amount of the palladium acetate is the 5 ‰ of 4- bromine benzocyclobutene molal quantity；The triphenylphosphine
Additional amount be 4- bromine benzocyclobutene molal quantity 10 ‰.
Embodiment 3:
A kind of synthetic method of 4- vinyl benzocyclobutene, comprising the following steps: be added in autoclave dissolved with carbonic acid
Then the solvent of potassium 4- bromine benzocyclobutene and catalyst is added in solvent, close kettle cover；Using in nitrogen displacement autoclave
Air three times, then passes to ethylene gas, and reaction pressure is made to reach 4MPa, seals and is warming up to 80 DEG C, is stirred to react 6 hours,
Pressure drops to 2.5MPa, stops heating, obtains reaction solution, by reaction solution split-phase, obtains oily phase and water phase；Water phase is extracted with ether
It takes 2 times, obtained ether phase mutually merges with oil, is then cleaned 1 time with deionized water and saturated sodium chloride solution respectively, anhydrous sulphur
Sour sodium drying 4 hours or more, solvent was evaporated off in dry back spin, is condensed into pale yellow oily liquid, is carried out using high vacuum oil pump
Vacuum distillation purification, collects 75~80 DEG C of fraction, obtains colourless transparent oil liquid 4- vinyl benzocyclobutene, purity
Greater than 97%, yield 75.8%；The weight ratio of the 4- bromine benzocyclobutene and potassium carbonate is 2:1；The 4- bromine benzo ring
The weight ratio of butylene and solvent is 1:2；The solvent is the deionized water and organic solvent that weight ratio is 1:1；It is described organic molten
Agent is n,N-Dimethylformamide；The additional amount of the palladium acetate is the 3 ‰ of 4- bromine benzocyclobutene molal quantity；The triphenyl
The additional amount of phosphine is the 6 ‰ of 4- bromine benzocyclobutene molal quantity.
Embodiment 4:
In 1000ml autoclave, potassium carbonate 181.2g, deionized water 175g, n,N-Dimethylformamide is added
175g is stirred evenly, and reactant is white casse shape at this time, opens heating, is warming up to 50 DEG C, makes solid dissolution completely, then
It is slowly added to 4- bromine benzocyclobutene 200g, palladium acetate 0.74g, triphenylphosphine 1.72g, closes kettle cover；
Three times using air in nitrogen displacement autoclave, high pressure ethylene gas is then passed to, pressure in kettle is made to reach 4MPa,
Close all valves, it is ensured that after autoclave is fully sealed, start to warm up, be stirred to react under 80 DEG C or so 6 hours, pressure will drop
To 2.5MPa or so, heating is closed at this time, starts to cool down, be cooled to room temperature to reaction kettle, carefully open drain tap, discharge kettle
After interior pressure, i.e., openable autoclave；
Reaction solution is moved in separatory funnel, two layers of reaction solution point, upper layer is oily phase (product phase), and lower layer is water phase；
Product is mutually separated, water phase discards after being extracted 2 times with 500ml ether；After the ether phase of extraction mutually merges with product, 1000ml is used
Deionization is washed one time, and 1000ml saturated sodium chloride solution is washed one time, and anhydrous sodium sulfate is 4 hours dry or more；It is rotated after drying
Solvent is removed, pale yellow oily liquid is condensed into；Vacuum distillation purification is carried out using high vacuum oil pump, 75~80 DEG C of collection evaporates
Point, obtaining product is colourless transparent oil liquid 102.8g, and GC detects purity and is greater than 97%, and yield is about 72.3%.
Embodiment 5:
In a high pressure reaction kettle, potassium carbonate 250g, deionized water 500g, n,N-Dimethylformamide 500g, stirring is added
Uniformly, reactant is white casse shape at this time, opens heating, is warming up to 50 DEG C, makes solid dissolution completely, is then slowly added into 4-
Bromine benzocyclobutene 500g, palladium acetate 1.84g, triphenylphosphine 4.3g close kettle cover；
Three times using air in nitrogen displacement autoclave, high pressure ethylene gas is then passed to, pressure in kettle is made to reach 4MPa,
Close all valves, it is ensured that after autoclave is fully sealed, start to warm up, be stirred to react under 80 DEG C or so 6 hours, pressure will drop
To 2.5MPa or so, heating is closed at this time, starts to cool down, be cooled to room temperature to reaction kettle, carefully open drain tap, discharge kettle
After interior pressure, i.e., openable autoclave；
Reaction solution is moved in separatory funnel, two layers of reaction solution point, upper layer is oily phase (product phase), and lower layer is water phase；
Product is mutually separated, water phase discards after being extracted 2 times with 1000ml ether；After the ether phase of extraction mutually merges with product, use
1500ml deionization is washed one time, and 1500ml saturated sodium chloride solution is washed one time, and anhydrous sodium sulfate is 4 hours dry or more；It is dry
Solvent is evaporated off in back spin, is condensed into pale yellow oily liquid；Vacuum distillation purification is carried out using high vacuum oil pump, collects 75~80
DEG C fraction, obtain product be colourless transparent oil liquid 267g, GC detect purity be greater than 97%, yield is about 75.8%.
Embodiment 6:
In a high pressure reaction kettle, potassium carbonate 500g is added, deionized water 1500g, n,N-Dimethylformamide 1500g are stirred
It mixes uniformly, reactant is white casse shape at this time, opens heating, is warming up to 50 DEG C, makes solid dissolution completely, is then slowly added into
4- bromine benzocyclobutene 1000g, palladium acetate 6.13g, triphenylphosphine 11.47g close kettle cover；
Three times using air in nitrogen displacement autoclave, high pressure ethylene gas is then passed to, pressure in kettle is made to reach 5MPa,
Close all valves, it is ensured that after autoclave is fully sealed, start to warm up, be stirred to react under 80 DEG C or so 6 hours, pressure will drop
To 2.5MPa or so, heating is closed at this time, starts to cool down, be cooled to room temperature to reaction kettle, carefully open drain tap, discharge kettle
After interior pressure, i.e., openable autoclave；
Reaction solution is moved in separatory funnel, two layers of reaction solution point, upper layer is oily phase (product phase), and lower layer is water phase；
Product is mutually separated, water phase discards after being extracted 2 times with 1500ml ether；After the ether phase of extraction mutually merges with product, use
2000ml deionization is washed one time, and 2000ml saturated sodium chloride solution is washed one time, and anhydrous sodium sulfate is 4 hours dry or more；It is dry
Solvent is evaporated off in back spin, is condensed into pale yellow oily liquid；Vacuum distillation purification is carried out using high vacuum oil pump, collects 75~80
DEG C fraction, obtain product be colourless transparent oil liquid 530g, GC detect purity be greater than 97%, yield is about 75.2%.
Embodiment 7:
A kind of synthetic method of 4- vinyl benzocyclobutene, comprising the following steps: by sodium acetate, deionized water and organic
Solvent is mixed, and is warming up to 60 DEG C, dissolution obtains solvent completely；Solvent is added in autoclave, then by 4- bromine benzo ring
Butylene and catalyst are added in solvent, close kettle cover；Three times using air in nitrogen displacement autoclave, ethylene gas is then passed to
Body makes reaction pressure reach 5MPa, seals and is warming up to 75 DEG C, is stirred to react 7 hours, obtains reaction solution, by reaction solution split-phase,
Obtain oily phase and water phase；Water phase with ether extract 2 times, obtained ether phase with oil mutually merge, then respectively use deionized water with
Saturated sodium chloride solution is cleaned 1 time, and anhydrous sodium sulfate is 4 hours dry or more, and solvent is evaporated off in dry back spin, is condensed into faint yellow
Oily liquids carries out vacuum distillation purification using high vacuum oil pump, collects 75~80 DEG C of fraction, obtain colorless and transparent oily liquid
Body 4- vinyl benzocyclobutene, purity are greater than 97%, yield 74.8%；The 4- bromine benzocyclobutene and sodium acetate
Weight ratio is 3:1；The weight ratio of the 4- bromine benzocyclobutene and solvent is 1:3；The solvent be weight ratio be 1:1 go from
Sub- water and organic solvent；The organic solvent is tetrahydrofuran；The additional amount of the palladium acetate is 4- bromine benzocyclobutene mole
Several 3 ‰；The additional amount of the triphenylphosphine is the 6 ‰ of 4- bromine benzocyclobutene molal quantity.
Embodiment 8:
A kind of synthetic method of 4- vinyl benzocyclobutene, comprising the following steps: by potassium acetate, deionized water and organic
Solvent is mixed, and is warming up to 60 DEG C, dissolution obtains solvent completely；Solvent is added in autoclave, then by 4- bromine benzo ring
Butylene and catalyst are added in solvent, close kettle cover；Three times using air in nitrogen displacement autoclave, ethylene gas is then passed to
Body makes reaction pressure reach 6MPa, seals and is warming up to 80 DEG C, is stirred to react 7 hours, obtains reaction solution, by reaction solution split-phase,
Obtain oily phase and water phase；Water phase with ether extract 2 times, obtained ether phase with oil mutually merge, then respectively use deionized water with
Saturated sodium chloride solution is cleaned 1 time, and anhydrous sodium sulfate is 4 hours dry or more, and solvent is evaporated off in dry back spin, is condensed into faint yellow
Oily liquids carries out vacuum distillation purification using high vacuum oil pump, collects 75~80 DEG C of fraction, obtain colorless and transparent oily liquid
Body 4- vinyl benzocyclobutene, purity are greater than 97%, yield 75.1%；The 4- bromine benzocyclobutene and potassium acetate
Weight ratio is 2:1；The weight ratio of the 4- bromine benzocyclobutene and solvent is 1:2；The solvent be weight ratio be 1:1 go from
Sub- water and organic solvent；The organic solvent is tetrahydrofuran；The additional amount of the palladium acetate is 4- bromine benzocyclobutene mole
Several 5 ‰；The additional amount of the triphenylphosphine is the 7 ‰ of 4- bromine benzocyclobutene molal quantity.
In order to illustrate effect of the invention, it is as follows that inventor provides comparative experiments:
Comparative example 1:
The potassium carbonate of addition and the weight ratio of 4- bromine benzocyclobutene are 0.8:1, remaining parameter and the complete phase in example 1
Together, technical process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 95%, receives
Rate is 65%.
Comparative example 2:
The potassium carbonate of addition and the weight ratio of 4- bromine benzocyclobutene are 4:1, remaining parameter and the complete phase in example 1
Together, technical process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 95%, receives
Rate is 62%.
Comparative example 3:
The potassium carbonate of addition and the weight ratio of 4- bromine benzocyclobutene are 0.8:1, remaining parameter and the complete phase in example 2
Together, technical process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 94%, receives
Rate is 61%.
Comparative example 4:
The potassium carbonate of addition and the weight ratio of 4- bromine benzocyclobutene are 4:1, remaining parameter and the complete phase in example 2
Together, technical process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 94%, receives
Rate is 61.9%.
Comparative example 5:
The weight ratio of the 4- bromine benzocyclobutene and solvent is 1:1, remaining parameter and identical, the work in example 1
Skill process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 94%, yield is
63%.
Comparative example 6:
The weight ratio of the 4- bromine benzocyclobutene and solvent is 1:4, remaining parameter and identical, the work in example 1
Skill process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 94%, yield is
62%.
Comparative example 7:
The weight ratio of the 4- bromine benzocyclobutene and solvent is 1:1, remaining parameter and identical, the work in example 2
Skill process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 94%, yield is
65%.
Comparative example 8:
The weight ratio of the 4- bromine benzocyclobutene and solvent is 1:4, remaining parameter and identical, the work in example 2
Skill process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 92%, yield is
60%.
Comparative example 9:
The additional amount of the palladium acetate be 4- bromine benzocyclobutene molal quantity 1 ‰, remaining parameter with it is complete in example 1
Identical, technical process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 92%,
Yield is 65%.
Comparative example 10:
The additional amount of the palladium acetate be 4- bromine benzocyclobutene molal quantity 6 ‰, remaining parameter with it is complete in example 1
Identical, technical process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 92%,
Yield is 64%.
Comparative example 11:
The additional amount of the palladium acetate be 4- bromine benzocyclobutene molal quantity 1 ‰, remaining parameter with it is complete in example 2
Identical, technical process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 90%,
Yield is 62%.
Comparative example 12:
The additional amount of the palladium acetate be 4- bromine benzocyclobutene molal quantity 6 ‰, remaining parameter with it is complete in example 2
Identical, technical process is also identical, obtains the purity of colourless transparent oil liquid 4- vinyl benzocyclobutene less than 91%,
Yield is 63%.
Comparative example 13:
The additional amount of the triphenylphosphine be 4- bromine benzocyclobutene molal quantity 3 ‰, remaining parameter with it is complete in example 1
Exactly the same, technical process is also identical, and the purity for obtaining colourless transparent oil liquid 4- vinyl benzocyclobutene is less than
92%, yield 63.5%.
Comparative example 14:
The additional amount of the triphenylphosphine is the 11 ‰ of 4- bromine benzocyclobutene molal quantity, in remaining parameter and example 1
Identical, technical process is also identical, and the purity for obtaining colourless transparent oil liquid 4- vinyl benzocyclobutene is less than
93%, yield 64.5%.
Comparative example 15:
The additional amount of the triphenylphosphine be 4- bromine benzocyclobutene molal quantity 3 ‰, remaining parameter with it is complete in example 2
Exactly the same, technical process is also identical, and the purity for obtaining colourless transparent oil liquid 4- vinyl benzocyclobutene is less than
93%, yield 66.5%.
Comparative example 16:
The additional amount of the triphenylphosphine is the 11 ‰ of 4- bromine benzocyclobutene molal quantity, in remaining parameter and example 2
Identical, technical process is also identical, and the purity for obtaining colourless transparent oil liquid 4- vinyl benzocyclobutene is less than
93%, yield 64.8%.
Comparative example 17:
It is described to be warming up to 65 DEG C, remaining parameter with it is identical in example 1, technical process is also identical, obtains nothing
The purity of color transparent oily liquid 4- vinyl benzocyclobutene is less than 93%, yield 62.8%.
Comparative example 18:
It is described to be warming up to 95 DEG C, remaining parameter with it is identical in example 1, technical process is also identical, obtains nothing
The purity of color transparent oily liquid 4- vinyl benzocyclobutene is less than 93%, yield 63.6%.
Comparative example 19:
It is described to be warming up to 65 DEG C, remaining parameter with it is identical in example 2, technical process is also identical, obtains nothing
The purity of color transparent oily liquid 4- vinyl benzocyclobutene is less than 92%, yield 64.6%.
Comparative example 20:
It is described to be warming up to 95 DEG C, remaining parameter with it is identical in example 2, technical process is also identical, obtains nothing
The purity of color transparent oily liquid 4- vinyl benzocyclobutene is less than 92%, yield 63.9%.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (4)
1. a kind of synthetic method of 4- vinyl benzocyclobutene, which comprises the following steps:
4- bromine benzocyclobutene and catalyst are added dissolved in the solvent of acid binding agent, and are in nitrogen atmosphere, then
It is passed through ethylene gas, reaction pressure is made to reach 1~10MPa, seals and heats up and be stirred to react, reaction solution is obtained, at reaction solution
4- vinyl benzocyclobutene is obtained after reason；
The weight ratio of the 4- bromine benzocyclobutene and acid binding agent is 1~3:1；
The weight ratio of the 4- bromine benzocyclobutene and solvent is 1:1.5~3；
The solvent is the deionized water and organic solvent that weight ratio is 1:1；The organic solvent is n,N-Dimethylformamide；
The solvent dissolved with acid binding agent the preparation method comprises the following steps: by acid binding agent, deionized water and organic solvent be mixed, heating
To 50~60 DEG C, dissolution obtains solvent completely；The acid binding agent is potassium carbonate；
The catalyst is the palladium acetate and triphenylphosphine that molar ratio is 1:2~4；The additional amount of the palladium acetate be 4- bromobenzene simultaneously
The 2 of cyclobutane molal quantity~5 ‰；The additional amount of the triphenylphosphine is 4~the 10 ‰ of 4- bromine benzocyclobutene molal quantity；
The temperature of the heating is 70~90 DEG C；The time being stirred to react is 5~8 hours；It is stirred to react to pressure and drops to 0.5
Stop heating after~4MPa.
2. the synthetic method of 4- vinyl benzocyclobutene as described in claim 1, which is characterized in that the organic solvent replaces
It is changed to any one in acetonitrile, tetrahydrofuran, toluene, methanol and 1,4- dioxane.
3. the synthetic method of 4- vinyl benzocyclobutene as described in claim 1, which is characterized in that the acid binding agent replacement
For any one in potassium acetate, sodium acetate.
4. the synthetic method of 4- vinyl benzocyclobutene as described in claim 1, which is characterized in that the reaction solution processing
Process are as follows: by reaction solution split-phase, obtain it is oily mutually and water phase；Water phase is extracted with ether, and obtained ether phase mutually merges with oil, so
It is cleaned respectively with deionized water and saturated sodium chloride solution afterwards, anhydrous sodium sulfate is dry, and solvent is evaporated off in dry back spin, is condensed into
Pale yellow oily liquid carries out vacuum distillation purification using high vacuum oil pump, collects 75~80 DEG C of fraction, obtain colorless and transparent
Oily liquids 4- vinyl benzocyclobutene.
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| CN201610828094.0A CN106397085B (en) | 2016-09-18 | 2016-09-18 | The synthetic method of 4- vinyl benzocyclobutene |
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| CN201610828094.0A CN106397085B (en) | 2016-09-18 | 2016-09-18 | The synthetic method of 4- vinyl benzocyclobutene |
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| CN108083963B (en) * | 2017-12-26 | 2020-08-28 | 中国工程物理研究院激光聚变研究中心 | Synthetic method of diarylethene |
| WO2022242292A1 (en) * | 2021-05-21 | 2022-11-24 | 华为技术有限公司 | Benzocyclobutene monomer, benzocyclobutene resin, preparation method therefor, low dielectric constant material, and semiconductor device |
| CN114478178B (en) * | 2022-04-06 | 2022-07-26 | 华南理工大学 | Benzocyclobutene-substituted triethylene cyclohexane compound and preparation method thereof, and organic dielectric material and preparation method thereof |
| CN115141157A (en) * | 2022-06-27 | 2022-10-04 | 佳化化学科技发展（上海）有限公司 | Isocyanuric acid triacrylate, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136069A (en) * | 1991-03-28 | 1992-08-04 | The Dow Chemical Company | Process for preparing vinylically-unsaturated compounds (II) |
| WO2013096918A1 (en) * | 2011-12-22 | 2013-06-27 | Georgia Tech Research Corporation | Crosslinking triscarbazole hole transport polymers |
| CN104701238A (en) * | 2013-11-14 | 2015-06-10 | 罗门哈斯电子材料有限公司 | Gap-fill methods |
-
2016
- 2016-09-18 CN CN201610828094.0A patent/CN106397085B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136069A (en) * | 1991-03-28 | 1992-08-04 | The Dow Chemical Company | Process for preparing vinylically-unsaturated compounds (II) |
| WO2013096918A1 (en) * | 2011-12-22 | 2013-06-27 | Georgia Tech Research Corporation | Crosslinking triscarbazole hole transport polymers |
| CN104701238A (en) * | 2013-11-14 | 2015-06-10 | 罗门哈斯电子材料有限公司 | Gap-fill methods |
Non-Patent Citations (1)
| Title |
|---|
| "苯并环丁烯类化合物的合成";徐婷婷等;《高分子通报》;20061130(第11期);第75页 |
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