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CN-113512054-B - Benzocyclobutene functionalized organosilicon compound and preparation method thereof

CN113512054BCN 113512054 BCN113512054 BCN 113512054BCN-113512054-B

Abstract

The invention relates to the technical field of chemical materials, in particular to a benzocyclobutene-containing functionalized organosilicon compound and a preparation method thereof. The structure of the compound is shown as a formula (I): Wherein n is an integer from 2 to 8, R is one of (a) a substituted or unsubstituted C 1 ～C 6 alkyl group, and (b) a substituted or unsubstituted aryl group. The compound or the polymer obtained by copolymerizing the compound with other compounds containing unsaturated bonds has excellent thermal stability, mechanical property and dielectric property, can be used as a high-temperature resistant material, a high-performance composite material, an electronic packaging material, an aviation material and the like, and is applied to interlayer packaging of 5G/6G high-frequency PCB boards and chips and the like. The preparation method disclosed by the invention is simple, the raw materials are cheap and easy to obtain, the yield is high, the cost is low, and the preparation method is easy for mass production and application.

Inventors

  • ZHU YANYAN
  • HU HUAN
  • WANG CHAO
  • ZHENG JIE

Assignees

  • 天诺光电材料股份有限公司

Dates

Publication Date
20260505
Application Date
20210520

Claims (8)

  1. 1. A benzocyclobutene-containing functionalized organosilicon compound, characterized by the structure shown in formula (I): Formula (I) Wherein n is an integer of 2-8, R is one of the following: (a) Alkyl of substituted or unsubstituted C 1 ~C 6 ; (b) A substituted or unsubstituted phenyl group; The substituent means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of C 1 ~C 4 alkyl, unsubstituted phenyl.
  2. 2. A process for producing a compound according to claim 1, which comprises the steps of starting vinylsilane, 4- (1, 1-dimethyl-1-hydro-yl) silicon-based benzocyclobutene, chloroplatinic acid, toluene; Wherein, the mol ratio of the vinyl silane to the 4- (1, 1-dimethyl-1-hydrogen) silicon-based benzocyclobutene to the chloroplatinic acid is 1:3.5-6:3 multiplied by 10 -3 ～1×10 -2 .
  3. 3. The method for preparing the compound according to claim 2, comprising the following steps: Sequentially adding the raw materials into a reactor, introducing nitrogen for protection for 10-30 min, continuously stirring, continuously reacting for 18-60 h at the temperature of 60-90 o ℃, cooling to room temperature after the reaction is finished, removing the solvent under the conditions of the pressure of-0.09 to-0.095 MPa and the temperature of 30-40 o ℃, and purifying by a column chromatography or crystallization method to obtain the catalyst.
  4. 4. The method for producing a polymer of a compound according to claim 1, wherein the compound or the prepolymer containing the compound is heated to 165 to 200 o C and cured for 2 to 24 hours.
  5. 5. The method for preparing the compound-containing prepolymer is characterized by comprising the steps of adding the compound and trimethylbenzene into an anaerobic bottle, introducing nitrogen for 10-30 minutes, heating to 155-165- o ℃ for prepolymerization reaction for 15-55 hours, cooling to room temperature, and removing the trimethylbenzene under the conditions of pressure of-0.09 to-0.095 MPa and temperature of 85-90 o ℃ to obtain the prepolymer.
  6. 6. The method for preparing the polymer of the compound according to claim 5, wherein the obtained prepolymer is subjected to a curing reaction, and the method comprises the specific steps of preparing the obtained prepolymer into a toluene solution with the concentration of 0.5-1%, homogenizing the toluene solution at 2000-3000 r/min for film formation, heating the toluene solution at the temperature of 50-60 o ℃ for 8-12 hours, heating the toluene solution at the temperature of 170-180 o ℃ for 3-4 hours, heating the toluene solution at the temperature of 200-210 o ℃ for 2-4 hours, heating the toluene solution at the temperature of 220-230 o ℃ for 2-5 hours, and keeping the toluene solution at the temperature of 240-250 o ℃ for 1-3 hours.
  7. 7. The method for producing a polymer of a compound according to claim 6, wherein the step of subjecting the obtained prepolymer to a curing reaction comprises the step of heating the obtained prepolymer in a plurality of stages to carry out the curing reaction: The curing reaction is carried out in 4 stages, wherein the first stage is to heat up to 150-160 o ℃ for 3-4 hours, the second stage is to heat up to 180-200 o ℃ for 3-5 hours, the third stage is to heat up to 210-220 o ℃ for 1-2 hours, and the fourth stage is to heat up to 240-250 o ℃ for 1-2 hours.
  8. 8. The compound of claim 1, and the application of the polymer prepared by the method of any one of claims 4-7 in processing of 5G/6G high-frequency PCB and chips.

Description

Benzocyclobutene functionalized organosilicon compound and preparation method thereof Technical Field The invention relates to the technical field of chemical materials, in particular to a benzocyclobutene functionalized organosilicon compound and a preparation method thereof. Background The benzocyclobutene (BCB) material has the characteristics of excellent high and low temperature resistance, low dielectric property, low loss, good air tightness, irradiation resistance, particularly excellent film forming property, moisture resistance and the like, and is widely applied to the field of electronic packaging. The BCB monomer is converted into a conjugated diene structure after being heated, and the highly crosslinked polymer is obtained through free radical polymerization and Diels-Alder reaction. Tetramethyl divinyl siloxane bridged benzocyclobutene (DVSBCB for short) developed by the dow chemical company (US 5882836) is shown below. The chemical structural formula is shown in the formula, and the resin has low dielectric constant and dielectric loss and has been widely applied to integrated circuit packaging. Due to the rapid development of the semiconductor industry at high frequency and high speed, DVSBCB resins have hardly satisfied the requirements of next-generation electronic components on dielectric insulation materials. In the prior art, a lot of reports about benzocyclobutene resin at home and abroad are provided, such as US5882836, US5217568, US5136069, journal of Polymer Science, part A Polymer Chemistry,2011,49,381-391, chinese patent CNL200710111698.4 and the like, benzocyclobutene resin prepared by using BCB intermediate through a silicon hydride, HECK or Grignard reaction shows better electrical property and thermal property, but with the development requirement of high frequency and high speed, low dielectric material with dielectric loss of 10 -4 is required for 5G/6G at present, and the application of the material in the semiconductor industry is limited under the conditions of high frequency and high speed, wherein the dielectric constant of the conventional commercially available DVSBCB resin at home and abroad is 2.65, and the dielectric loss is 10 -3-10-2. There is a strong need in the art to develop a high performance low dielectric material with dielectric loss on the order of 10 -4 at high frequencies. Disclosure of Invention The main object of the present invention is to provide a benzocyclobutene-containing functionalized organosilicon compound and a preparation method thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: the invention provides a benzocyclobutene-containing functionalized organosilicon compound, the structure of which is shown as a formula (I): Wherein n is an integer from 2 to 8, R is one of the following: (a) Alkyl of substituted or unsubstituted C 1～C6; (b) Substituted or unsubstituted aryl. Further, the substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of C 1～C4 alkyl, unsubstituted phenyl. The invention also provides a preparation method of the compound, which comprises the following raw materials of vinyl silane, 4- (1, 1-dimethyl-1-hydrogen radical) silicon-based benzocyclobutene, chloroplatinic acid and toluene; Wherein, the mol ratio of vinylsilane, 4- (1, 1-dimethyl-1-hydrogen) silicon-based benzocyclobutene (4-DMHSBCB) and chloroplatinic acid is 1:3.5-6:3 multiplied by 10 -3～1×10-2. Further, the method specifically comprises the following steps: Sequentially adding the raw materials into a reactor, introducing nitrogen for protection for 10-30 min, continuously stirring, continuously reacting for 18-60 h at the temperature of 60-90 ℃, cooling to room temperature after the reaction is finished, removing the solvent under the conditions of the pressure of-0.09 to-0.095 MPa and the temperature of 30-40 ℃, and purifying by a column chromatography or crystallization method to obtain the catalyst. The invention also provides a preparation method of the polymer of the compound, which comprises the step of heating the compound or the prepolymer containing the compound to 165-200 ℃ for curing reaction for 2-24 h. The preparation method of the prepolymer containing the compound comprises the steps of adding the compound or the mixture containing the compound and trimethylbenzene into an anaerobic bottle, introducing nitrogen for 10-30 minutes, heating to 155-165 ℃ for prepolymerization reaction for 15-55 h, cooling to room temperature, and removing the trimethylbenzene under the conditions of pressure of-0.09 to-0.095 MPa and temperature of 85-90 ℃ to obtain the prepolymer. Further, the obtained prepolymer is subjected to a curing reaction, and the method comprises the specific steps of preparing the obtained prepolymer into a toluene solution with the concentration of 0.5-1%, homogenizing the toluene solution at 2000-3000