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CN-121991353-A - Benzocyclobutene functionalized organic-inorganic hybrid microsphere and preparation method and application thereof

CN121991353ACN 121991353 ACN121991353 ACN 121991353ACN-121991353-A

Abstract

The invention discloses benzocyclobutene functionalized organic-inorganic hybrid microspheres and a preparation method and application thereof, and relates to the technical field of modified materials. The hybrid microsphere is a siloxane hybrid microsphere prepared by hydrolytic condensation of a silane precursor, wherein the hybrid microsphere is internally provided with a ladder-cage polysilsesquioxane structure, when the microsphere is added into BCB resin, the effect of obviously reducing the dielectric constant of the BCB resin can be realized through the mutual cooperation between a nanoscale cavity in the cage structure and the low-polarizability effect of the ladder structure, and the surface of the microsphere contains a large number of benzocyclobutene functional groups, so that the crosslinking density of a composite material and the dispersibility and compatibility of the hybrid microsphere in the BCB resin can be obviously improved, the adverse effect of a modified material on the performance of the BCB resin can be obviously improved, and the hybrid microsphere is suitable for large-scale application in the dielectric reduction modification of the BCB resin.

Inventors

  • PENG QIUXIA
  • ZHONG JIACHUN
  • PU ZEJUN
  • MENG CHIHAN

Assignees

  • 四川轻化工大学

Dates

Publication Date
20260508
Application Date
20260319

Claims (10)

  1. 1. The benzocyclobutene functionalized organic-inorganic hybrid microsphere is characterized in that the hybrid microsphere is a polysilsesquioxane composite microsphere with a cage-type and ladder-type structure, which is prepared by hydrolysis and condensation of a silane precursor, wherein the surface of the hybrid microsphere contains benzocyclobutene functional groups; the silane precursor has a structure shown in a formula I: , I; Wherein R 1 is one or the absence of C 1 ~C 6 alkylene, and R 2 ~R 4 is one of C 1 ~C 6 alkyl respectively.
  2. 2. The benzocyclobutene-functionalized organic-inorganic hybrid microsphere according to claim 1, wherein the hybrid microsphere has a particle size of 0.2-3 μm, preferably a particle size of 1±0.1 μm.
  3. 3. The benzocyclobutene-functionalized organic-inorganic hybrid microsphere of claim 1, wherein the hybrid microsphere is prepared by cohydrolytic condensation of a silane precursor and a silane coupling agent.
  4. 4. The benzocyclobutene-functionalized organic-inorganic hybrid microsphere according to claim 3, wherein the molar ratio of the silane precursor to the silane coupling agent is 1:0-0.3, and preferably the molar ratio of the silane precursor to the silane coupling agent is 1:0-0.1.
  5. 5. A method of preparing benzocyclobutene-functionalized organic-inorganic hybrid microspheres according to any one of claims 1 to 4, comprising the steps of: (1) Adding 4-halogenated benzocyclobutene, trialkoxysilane containing vinyl, an acid binding agent, a palladium catalyst and an organophosphorus ligand into an organic solvent, and performing Heck coupling reaction under the inert atmosphere at 80-120 ℃ to obtain a silane precursor; (2) And (3) uniformly stirring and mixing a silane precursor, a silane coupling agent, an alkaline compound and a solvent, and then performing hydrolytic condensation reaction at the temperature of 0-100 ℃ to obtain the benzocyclobutene functionalized organic-inorganic hybrid microsphere.
  6. 6. The method according to claim 5, wherein in the step (1), the amount ratio of the substances including 4-halobenzocyclobutene, vinyl-containing trialkoxysilane, palladium-based catalyst, organic phosphine ligand and basic compound is 1.0:1.0 to 2.0:0.001 to 0.05:0.01 to 0.5:1.0 to 3.0.
  7. 7. The method according to claim 5, wherein in the step (2), the hydrolysis-condensation reaction temperature is 20 to 50 ℃, more preferably 20 to 40 ℃.
  8. 8. The method according to claim 5, wherein in the step (2), the amount of the basic compound is 0.1 to 0.5 times the mass of the silane precursor.
  9. 9. Use of the benzocyclobutene-functionalized organic-inorganic hybrid microspheres of any one of claims 1 to 4 in the preparation of a low dielectric constant benzocyclobutene-based resin composite.
  10. 10. Use according to claim 9, characterized in that the hybrid microspheres are added in an amount of 2-10wt%, preferably 2-5wt%, to the benzocyclobutene-based resin composite.

Description

Benzocyclobutene functionalized organic-inorganic hybrid microsphere and preparation method and application thereof Technical Field The invention relates to the technical field of modified materials, mainly relates to the technical field of polymer modified materials, and in particular relates to a benzocyclobutene functionalized organic-inorganic hybrid microsphere, a preparation method and application thereof. Background Benzocyclobutene (BCB) resin, particularly divinyl siloxane-bisbenzocyclobutene resin (DVSBCB), has a low dielectric constant (about 2.65) after curing, good thermal stability, and low water absorption, and becomes a core substrate in the fields of high-frequency communication, microelectronic packaging, copper-clad plates, and the like. However, with the continuous development of 5G and next generation communication technologies, the requirements on dielectric properties of materials are further increased. Therefore, it is required to reduce the dielectric constant of the BCB resin to 2.40 or less, and to maintain excellent thermal stability, dimensional stability and transparency of the BCB resin, and to avoid problems such as reduced compatibility and deteriorated performance due to the addition of the filler. The traditional dielectric reducing modification method of the BCB resin mainly comprises the step of introducing fluorine atoms or bulky groups into the molecular structure of the resin, and the method can reduce the dielectric constant, but has complex synthesis steps, high cost and possibly reduced thermal stability of the material. Another common method is to add inorganic fillers such as polyhedral oligomeric silsesquioxanes (POSS), silica, etc. to resins, however, these conventional inorganic fillers have poor compatibility with the resin matrix due to lack of chemical bonding sites with the resin on the surface, so that agglomeration easily occurs in the resin, resulting in problems of reduced transparency, increased dielectric loss, and significantly increased thermal expansion coefficient of the composite material. In addition, there are also prior art ways to achieve reduced dielectric modification of BCB resins by benzocyclobutene functionalization of nanofillers as well as hybrid fillers. However, the existing benzocyclobutene functionalized nano-filler preparation often needs expensive raw materials, and has the problems of low yield and purity and instability. The preparation of the hybrid filler requires high-temperature reaction or uses a surfactant to regulate the morphology, so that the problems of complex process and possibly influence on the material performance due to residual impurities are caused. Meanwhile, the existing dielectric lowering modification method of the BCB resin has the problems that dielectric lowering efficiency is limited due to low addition amount, and a higher filler addition amount (more than 10 wt%) is generally required to realize that dielectric constant is reduced to below 2.40 and mechanical property is degraded. Chinese patent CN108516986a discloses a benzocyclobutene functionalized tetra (dimethylsiloxy) silane and a method for preparing the same, which introduces benzocyclobutene functional groups into a siloxane compound by a hydrosilation reaction for preparing a silicone resin. However, the benzocyclobutene functionalized tetra (dimethylsiloxy) silane prepared by the patent is a monomer compound, has insufficient dispersion performance and compatibility in resin, and has the problems of easy agglomeration and poor dielectric reduction effect. Chinese patent CN107987278a discloses a benzocyclobutene functionalized silicone resin and a method for preparing the same. This patent uses Piers-Rubinsztajn (P-R) polycondensation to prepare organosilicon polymers (linear or hyperbranched structures) containing benzocyclobutene functionality using compounds containing silicon-hydrogen bonds (which must be present) and organosilicon compounds containing siloxy groups. The method requires complex raw material proportion, and the product structure is not easy to control accurately, so that the problems of poor dielectric reduction effect and deterioration of mechanical properties of modified resin exist. Therefore, a modified material which has good compatibility with benzocyclobutene resin, can obviously reduce dielectric effect and has simple preparation process is urgently needed to realize efficient modification of BCB resin so as to solve the problems of complex process, poor dispersibility and compatibility and low dielectric efficiency in the existing modification process. Disclosure of Invention The invention aims to solve the problems of complex preparation process, poor dispersibility and compatibility and low dielectric efficiency of the traditional dielectric reducing modified material of BCB resin, and provides a benzocyclobutene functionalized organic-inorganic hybrid microsphere and a preparation method and application ther