CN114316271A - Linear benzocyclobutene polysiloxane resin - Google Patents
Linear benzocyclobutene polysiloxane resin Download PDFInfo
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- CN114316271A CN114316271A CN202111388230.6A CN202111388230A CN114316271A CN 114316271 A CN114316271 A CN 114316271A CN 202111388230 A CN202111388230 A CN 202111388230A CN 114316271 A CN114316271 A CN 114316271A
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Abstract
The invention relates to the technical field of resin materials, and particularly relates to a linear benzocyclobutene-based polysiloxane resin. The resin structure is shown as the following formula (I):
Description
Technical Field
The invention relates to the technical field of resin materials, and particularly relates to a linear benzocyclobutene-based polysiloxane resin.
Background
With the rapid development of the semiconductor industry, the development and development of high-performance, low-dielectric and low-loss materials are highly regarded. Due to the development demand of high frequency and high speed, the size of the very large scale integrated circuit is gradually reduced and the link lines inside the chip are more and more dense, which results in the transmission delay and cross interference of signals, and the demand for high performance low dielectric and low loss materials is increasingly urgent. In order to solve these problems, materials are required to satisfy a combination of properties such as low dielectric constant, low loss, high mechanical strength, high thermal stability, and low thermal expansion.
The applicant previously filed patent application CN113480735A (published 2021, 10/08) which discloses a benzocyclobutene-based functionalized silicone resin having the following chemical structural formula:
the resin has the excellent performances of low dielectric, low loss, high thermal stability, low thermal expansion and the like. However, the method still has some defects, such as that the precursor DMBMOS is synthesized by adopting a Grignard method, BCB magnesium bromide has high activity to react with dimethyl dimethoxy silane, a double BCB byproduct can be generated, the boiling point of the byproduct is not greatly different from that of DMBMOS, the DMBMOS is difficult to purify, and the subsequent hydrolyzed polymer proportion and performance difference are caused; the thermal stability and low thermal expansion properties of the resin still need to be further improved.
Disclosure of Invention
The invention mainly aims to provide a linear benzocyclobutene-based polysiloxane resin which has better thermal stability and low thermal expansion performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a linear benzocyclobutene-based polysiloxane resin, which has a structure shown in the following formula (I):
wherein x is an integer of not less than 1, and y is an integer of not less than 0; r is any one of the following:
(a) substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted alkenyl having 2 to 6 carbon atoms, wherein said substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, or a phenyl group which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms for 1 to 3 hydrogen atoms on the phenyl ring;
(b) substituted or unsubstituted phenyl; the substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, and an unsubstituted phenyl group.
Further, the resin is obtained by end capping dibenzocyclobutenyl dimethoxysilane (DBDMOS) or dimethoxyvinyl organosilane with dimethyl benzocyclobutene vinylmethoxysilane (DMBVMOS) after hydrolytic condensation under the catalysis of acid or alkali.
Further, the preparation method of the dimethylbenzocyclobutene vinylmethoxysilane comprises the following steps: under dry conditions, dimethylvinylmethoxysilane and 4-bromobenzocyclobutene are prepared by HECK reaction in a solvent under inert gas.
The invention also provides application of the linear benzocyclobutene-based polysiloxane resin in preparation of materials with high thermal stability, low thermal expansion performance and low dielectric constant.
Compared with the prior art, the invention has the following advantages:
1) the linear benzocyclobutene polysiloxane resin has low dielectric and low loss, and has better thermal stability and low thermal expansion performance; can be used for preparing materials with high thermal stability, low thermal expansion performance and low dielectric constant.
2) The linear benzocyclobutene-based polysiloxane resin is obtained by end capping with DMBVMOS; the DMBVMOS is synthesized by adopting an HECK reaction, has high yield and easy purification, and is convenient for mass synthesis of linear benzocyclobutene-based polysiloxane resin.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
Preparation of Dimethylbenzocyclobutenylmethoxysilane (DMBVMOS): adding 4-bromobenzocyclobutene (10mmol), dimethylvinylmethoxysilane (10mmol), triethylamine (11mmol), dry acetonitrile (100mL) and palladium acetate (0.1mmol) into a 250mL eggplant-shaped bottle in a nitrogen atmosphere, quenching the reaction after the reaction is finished, removing solids by suction filtration, washing the solids with n-hexane for three times, diluting the filtrate with n-hexane after rotary evaporation and concentration, carrying out suction filtration on silica gel, removing the solvent by rotary evaporation and concentration of the filtrate, and then carrying out reduced pressure distillation on an oil pump to obtain colorless transparent liquid with the yield of 79%. The structure is characterized as follows:1H NMR(600MHz,CDCl3)δ(ppm):7.38-7.36(d,1H,ArH),7.32(s,1H,ArH),7.10-7.09(d,1H,ArH),6.71-6.65(d,1H,＝CH-),6.1-6.06(d,1H,＝CH-),3.55(s,3H,-CH2CH2-),3.19(s,4H,-CH2CH2-).0.1(s,6H,Si-CH3)。
preparation of dibenzocyclobutenyl dimethoxysilane (DBDMOS): adding 4-bromobenzocyclobutene (10mmol), tetramethoxysilane (5mmol), magnesium strip (11mmol), catalytic amount of iodine and dry tetrahydrofuran (100mL) into a 250mL eggplant-shaped bottle in a nitrogen atmosphere, quenching the reaction after the reaction is finished, removing solids by suction filtration, washing the solids with n-hexane for three times, diluting the filtrate with n-hexane after rotary evaporation and concentration, carrying out suction filtration on silica gel, removing the solvent by rotary evaporation and concentration of the filtrate, and then carrying out vacuum distillation on an oil pump to obtain colorless transparent liquid with the yield of 79%. The structure is characterized as follows:
1H NMR(600MHz,CDCl3)δ(ppm):7.38-7.36(d,2H,ArH),7.32(s,2H,ArH),7.10-7.09(d,2H,ArH),3.55(s,6H,-CH2CH2-)3.19(s,8H,-CH2CH2-)。
example 2
Preparation of linear benzocyclobutene-based polysiloxane resin:
adding 0.1g of 10mmol of DBDMOS, 1mmol of methyl vinyl dimethoxysilane and 0.1g of aqueous solution (1 wt%) of tetramethyl ammonium hydroxide pentahydrate into a 100mL single-neck eggplant-shaped bottle, stirring uniformly at room temperature, stirring for reaction for 2h at 50 ℃ in an oil bath, adding 0.1mmol of dimethyl benzocyclobutene-based methoxysilane (DMBVMOS) for end capping, and heating to 125 ℃ to decompose the catalyst to obtain a light yellow flowable viscous liquid PDBS-r-PDMS random copolymer, wherein the molecular weight is 4100, and the molecular weight distribution is 7.1.
Through a dielectric test, the dielectric constant of the PDBS-r-PDMS condensate is 2.61 and the dielectric loss is 0.00095 under 20 GHz; t is5％473 deg.C; the coefficient of thermal expansion is 41 ppm/. degree.C. @20 ℃.
Example 3
Preparation of linear benzocyclobutene-based polysiloxane resin:
adding 0.1g of aqueous solution (1 wt%) of 10mmol of DBDMOS, 5mmol of methylvinyldimethoxysilane and tetramethylammonium hydroxide pentahydrate into a 100mL single-neck eggplant-shaped bottle, uniformly stirring at room temperature, stirring at 50 ℃ in an oil bath for reaction for 2h, adding 0.1mmol of Dimethylbenzocyclobutenylmethoxysilane (DMBVMOS) for end capping, and heating to 125 ℃ to decompose the catalyst to obtain a pale yellow flowable viscous liquid PDBS-r-PDMS random copolymer, wherein the molecular weight is 8900 and the molecular weight distribution is 7.3.
Through a dielectric test, the dielectric constant of the PDBS-r-PDMS condensate is 2.61 and the dielectric loss is 0.00095 under 20 GHz; t is5％473 deg.C; the coefficient of thermal expansion is 41 ppm/. degree.C. @20 ℃.
Example 4
Preparation of linear benzocyclobutene-based polysiloxane resin:
in a 100mL single-neck eggplant-shaped bottle, 0.1g of 10mmol of DBDMOS, 1mmol of vinylphenyldimethoxysilane and 0.1g of aqueous solution (1 wt%) of tetramethylammonium hydroxide pentahydrate are added, the mixture is stirred uniformly at room temperature, after stirring reaction for 2h at 50 ℃ in an oil bath, 0.1mmol of Dimethylbenzocyclobutenylmethoxysilane (DMBVMOS) is added for end capping, and then the temperature is raised to 125 ℃ to decompose the catalyst, so that a pale yellow flowable viscous liquid PDBS-r-PMPS random copolymer with the molecular weight of 6200 and the molecular weight distribution of 5.1 is obtained.
Through a dielectric test, the dielectric constant of a PDBS-r-PMPS cured product at 20GHz is 2.55, and the dielectric loss is 0.0008; t is5％472 deg.C; the coefficient of thermal expansion is 39 ppm/. degree.C. @20 ℃.
Example 5
Preparation of linear benzocyclobutene-based polysiloxane resin:
in a 100mL single-neck eggplant-shaped bottle, 0.1g of 10mmol of DBDMOS, 5mmol of vinyl phenyl dimethoxysilane and 0.1g of aqueous solution (1 wt%) of tetramethylammonium hydroxide pentahydrate are added, the mixture is stirred uniformly at room temperature, after stirring reaction for 2h at 50 ℃ in an oil bath, 0.1mmol of dimethyl benzocyclobutene-based methoxysilane (DMBVMOS) is added for end capping, and then the temperature is raised to 125 ℃ to decompose the catalyst, so that a light yellow flowable viscous liquid PDBS-r-PMPS random copolymer with the molecular weight of 7800 and the molecular weight distribution of 5.4 is obtained.
Through a dielectric test, the dielectric constant of a PDBS-r-PMPS cured product at 20GHz is 2.55, and the dielectric loss is 0.0008; t is5％472 deg.C; the coefficient of thermal expansion is 39 ppm/. degree.C. @20 ℃.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A linear benzocyclobutene-based polysiloxane resin, characterized in that its structure is represented by the following formula (I):
wherein x is an integer of not less than 1, and y is an integer of not less than 0; r is any one of the following:
(a) substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted alkenyl having 2 to 6 carbon atoms, wherein said substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, or a phenyl group which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms for 1 to 3 hydrogen atoms on the phenyl ring;
(b) substituted or unsubstituted phenyl; the substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, and an unsubstituted phenyl group.
2. The linear benzocyclobutene-based polysiloxane resin according to claim 1, which is obtained by end-capping dibenzocyclobutenyl dimethoxysilane or dimethoxyvinyl organosilane with dimethylbenzocyclobutene vinylmethoxysilane after hydrolytic condensation under the catalysis of acid or alkali.
3. The linear benzocyclobutene-based polysiloxane resin according to claim 1, characterized in that the method for preparing dimethylbenzocyclobutene vinylmethoxysilane comprises: under dry conditions, dimethylvinylmethoxysilane and 4-bromobenzocyclobutene are prepared by HECK reaction in a solvent under inert gas.
4. Use of the linear benzocyclobutene-based polysiloxane resin according to any one of claims 1 to 3 for preparing high thermal stability, low thermal expansion performance, low dielectric material.
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| CN116880126A (en) * | 2023-08-08 | 2023-10-13 | 西南科技大学 | Preparation and application of branched benzocyclobutenyl polysiloxane low dielectric loss photosensitive resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116880126A (en) * | 2023-08-08 | 2023-10-13 | 西南科技大学 | Preparation and application of branched benzocyclobutenyl polysiloxane low dielectric loss photosensitive resin |
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