CN101463042B - Silicon-containing benzocyclobutene resin, intermediate thereof and preparation of the resin and intermediate - Google Patents
Silicon-containing benzocyclobutene resin, intermediate thereof and preparation of the resin and intermediate Download PDFInfo
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Abstract
The invention discloses a silicon-containing benzocyclobutene resin and an intermediate thereof and preparation methods of the silicon-containing benzocyclobutene resin and the intermediate. The silicon-containing benzocyclobutene resin has a structural general formula as shown in formula I and the intermediate has the structural general formula as shown in formula II. The preparation method of an intermediate compound of the formula II is as follows: 4-bromobenzocyclobutene and divinylsiloxane as shown in formula III are dissolved in an organic solvent, and subject to a heating reaction under the action of a catalyst. The invention provides a direct monomer curing method and a B-phase resin curing method to prepare the silicon-containing benzocyclobutene resin as shown in the formula I. The resin has the advantages of high thermostability, water absorption rate lower than 0.20%, dielectric constant lower than 2.70 and dielectric loss lower than 3.3*10<-4>. The resin can be compounded with a photosensitive auxiliary agent to form photosensitive resin which can form a high-resolution photoetching pattern after being exposed to ultraviolet light, developed and cured, can be applied to preparing microelectronic package materials and has important application prospect.
Description
Technical field
The present invention relates to a kind of silicon-containing benzocyclobutene resin and midbody thereof and their preparation method.
Background technology
The benzocyclobutane olefine resin is by the organic cpds that contains the benzocyclobutene group ring-opening reaction to take place under heat effect at first to generate O-phthalic alkene quinone midbody; The thermosetting polymer resin that forms through each other crosslinking reaction then; Have excellent electrical isolation and dielectric properties, heat-resistant stability and chemicalstability; In addition, have good film-forming process performance and low water absorption etc., have good application prospects in high-tech sectors such as Aeronautics and Astronautics, space technology, electrical engineering and electric apparatus insulation and microelectronics Packaging.Typical application comprises, the layer insulation film in microelectronics Packaging field, multimedia messages carrier with film, microelectromechanical-systems (MEMS) with insulation film, liquid-crystal display planarization film, nonlinear optical material and high performance adhesive etc.
U.S. Dow Chemical company discloses a kind of benzocyclobutane olefine resin and preparation method thereof at 1988 (US 4783514A).This preparation method is through 4-bromobenzene and cyclobutene and contain bi-vinyl silicoorganic compound coupling generation benzocyclobutene resin monomer, and this monomer generates the benzocyclobutane olefine resin through being heating and curing.Thereafter, 1989 the said firm (US 4826997A) a kind of benzocyclobutane olefine resin that contains imide structure and preparation method thereof is disclosed.This preparation method generates benzocyclobutene monomer and resin thereof through 4-amido benzocyclobutene and the monomer generation dehydrating condensation that contains maleic anhydride or dianhydride structure.1992, the said firm (US 5136069A) disclosed a kind of by 4-bromobenzene and cyclobutene and the method that contains end-vinyl compound benzocyclobutene monomer again.This preparation method carries out the Heck reaction through 4-bromobenzene and cyclobutene and the organic cpds that contains end-vinyl under the catalysis of acid chloride and triphenylphosphine; Generate benzocyclobutene monomer; Comprise 1; 3-two (4 '-benzocyclobutane thiazolinyl) vinyl-1,3-tetramethyl disiloxane, (4 '-benzocyclobutane thiazolinyl) ethene, 1, two (4 '-benzocyclobutane thiazolinyl) ethene of 2-etc.
1999 Dow Chemical company (US 5882836A) disclose a kind of again by 1; 3-two (4 '-benzocyclobutane thiazolinyl) vinyl-1,3-tetramethyl disiloxane pass through the method that prepolymerization reaction generates high-molecular weight B-stage resin in the trimethylbenzene solution between refluxing.2000, the said firm (US6083661A) disclosed a kind of preparation method of photosensitivity benzocyclobutane olefine resin again; This preparation method is with 1; 3-two (4 '-benzocyclobutane thiazolinyl) vinyl-1; The resin that the B-stage resin of 3-tetramethyl disiloxane and the paired UV-light of photosensitivity triazo-compound complex group (I line 365nm) have photosensitivity; After exposure, development, curing, form high-resolution photoetching pattern, be widely used in fields such as high integration microelectronics Packaging.
In recent years; VLSI is towards the fast development of high performance, multifunction, microminiaturization, ultrathin typeization, high frequency direction, require supporting with it microelectronic packaging material also must heat-resisting towards height, low dielectric, directions such as low-loss, the low moisture absorption develop.Therefore, the new polymers packaged material of development excellent performance is significant.
Summary of the invention
The purpose of this invention is to provide a kind of silicon-containing benzocyclobutene resin and midbody thereof and their preparation method.
Silicon-containing benzocyclobutene monomer provided by the invention has the general structure shown in the formula II;
In the above-mentioned formula II general structure, A, B, C, D, E, F are one or more in Wasserstoffatoms, fluorine atom, methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl or the butyl; R
1Be methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, butyl phenyl, trifluoromethyl or 3,5-two trifluoromethyls; N is 0-10.
The method for preparing structure general formula shown in the formula II provided by the invention is that bi-vinyl siloxanes shown in 4-bromobenzene and cyclobutene and the formula III general structure is dissolved in the organic solvent reacting by heating under catalyst action;
In the above-mentioned formula III general structure, A, B, C, D, E, F are one or more in Wasserstoffatoms, fluorine atom, methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl or the butyl; R
1Be methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, butyl phenyl, trifluoromethyl or 3,5-two trifluoromethyls; N is 0-10.
In the above-mentioned method for preparing formula II structure general formula, the mol ratio of 4-bromobenzene and cyclobutene and said bi-vinyl siloxanes is 0.5-2, preferred 0.8-1.2.
Catalyst system therefor is sugar of lead, acid chloride, Palladous chloride, triphenylphosphine, three-(o-methyl-phenyl-) phosphine, three-(aminomethyl phenyl) phosphine or three-(p-methylphenyl) phosphine and the mixture that mixes by arbitrary proportion thereof; Used organic solvent is THF, ether, N, dinethylformamide, DMAC N,N, acetonitrile, diethylamine, Trimethylamine 99, triethylamine, tripropyl amine, Tri N-Propyl Amine or toluene and the mixture that mixes by arbitrary proportion thereof.Temperature of reaction is 5-200 ℃, preferred 5-120 ℃; Reaction times is 1-48 hour, preferred 12-24 hour.
In this method, used bi-vinyl siloxanes is 1,3-dimethyl--1,3-divinyl-1,3-phenylbenzene sily oxide, 1; 3-divinyl-1,3-tetraphenyl sily oxide, 1,3-dimethyl--1,3-divinyl-1,3-two (3 '-trifluoromethyl) sily oxide, 1; 3-divinyl-1,3-four (3 '-trifluoromethyl) sily oxide, 1,3-dimethyl--1,3-divinyl-1,3-two (3 ' 5 '-two trifluoromethyls) sily oxide, 1; 3-divinyl-1,3-four (3 ' 5 '-two trifluoromethyls) sily oxide, 1,5-dimethyl--1,5-divinyl-1,3; 5-tetraphenyl trisiloxanes, 1,5-divinyl-1,3,5-hexaphenyl trisiloxanes, 1,5-dimethyl--1; 5-divinyl-1,5-two (3 '-trifluoromethyl)-3,3-phenylbenzene trisiloxanes, 1,5-dimethyl--1,5-divinyl-1; 5-phenylbenzene-3,3-phenylbenzene trisiloxanes, 1,5-dimethyl--1,5-divinyl-1; 5-two (3 ' 5 '-two trifluoromethyls)-3,3-phenylbenzene trisiloxanes, 1,5-divinyl-1,5-four (3 '-trifluoromethyl)-3; 3-phenylbenzene trisiloxanes or 1,5-divinyl-1,5-four (3 ' 5 '-two trifluoromethyls)-3,3-phenylbenzene trisiloxanes.
Silicon-containing benzocyclobutene resin provided by the invention has general structure shown in the formula I;
Wherein, A, B, C, D, E, F are one or more in Wasserstoffatoms, fluorine atom, methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl or the butyl; R
1Be methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, butyl phenyl, trifluoromethyl or 3,5-two trifluoromethyls; Be preferably Wasserstoffatoms, fluorine atom, trifluoromethyl, methyl, phenyl, trifluoromethyl, 3 successively, 5-two trifluoromethyls; N=0-10, preferred n=0-2.
The method for preparing silicon-containing benzocyclobutene resin provided by the invention comprises two kinds of methods, is respectively direct curing of monomer and B-stage resin curing.
The direct curing of monomer provided by the present invention is that heat temperature raising is cooled to below 100 ℃ after 100-300 ℃ again with after the vacuum defoamation of silicon-containing benzocyclobutene monomer shown in the formula II.
In the direct curing of above-mentioned monomer, the temperature of vacuum defoamation is 80-120 ℃, and the deaeration time is 5-30min.This method is suitable for the preparation of the silicon-containing benzocyclobutene resin of various kinds, especially is suitable for preparing the cast of silicon-containing benzocyclobutene resin.Carry out the demoulding again after only needing to be cooled to above-mentioned silicon-containing benzocyclobutene resin below 100 ℃, promptly obtain completely crued benzocyclobutene resin cast part.
B-stage resin curing provided by the present invention may further comprise the steps:
1) silicon-containing benzocyclobutene monomer shown in the formula II is dissolved in the organic solvent; Obtain the monomeric solution of silicon-containing benzocyclobutene, be stirred and heated to 160-180 ℃, solution backflow 6-200 hour; Be cooled to room temperature; The monomeric solution of said silicon-containing benzocyclobutene is scattered in the alcoholic solvent, and collecting precipitation obtains partly solidified B-stage benzocyclobutane olefine resin;
2) with above-mentioned partly solidified B-stage benzocyclobutene resin dissolves in organic solvent; Carry out spin coating after being made into the solution of 10-60% solid content; Afterwards with this benzocyclobutane olefine resin heat temperature raising to 100-300 ℃, solidified 1-20 hour, be cooled to below 100 ℃.
In the above-mentioned B-stage resin curing, step 1) and step 2) in, the monomeric solid content of silicon-containing benzocyclobutene (also being the quality percentage composition) is 10～60%, preferred 20～30%.Used organic solvent is toluene, two toluene, m-xylene, trimethylbenzene, a trimethylbenzene, N, dinethylformamide, DMAC N,N or N-Methyl pyrrolidone and the mixture that mixes by arbitrary proportion thereof; Preferred two toluene or a trimethylbenzene.Used alcoholic solvent is C
1-C
10A kind of or its mixture that mixes by arbitrary proportion in the saturated fatty alcohol, particular methanol, ethanol, propyl alcohol, Virahol, the trimethyl carbinol or tertiary amyl alcohol and the mixture that mixes by arbitrary proportion thereof.
In the step 1) of above-mentioned B-stage resin curing,, solution stops the reaction of solution reflux when reaching suitable viscosity.This method is suitable for preparing the silicon-containing benzocyclobutene resin of various kinds, especially is suitable for preparing silicon-containing benzocyclobutene resin coating or film.Only need step 2) in B-stage benzocyclobutene resin solution be spun on clean substrate surface; Like silicon single crystal, polysilicon, metallic aluminium, quartz, glass, copper printed circuit board or pottery etc., promptly obtain being coated on the completely crued benzocyclobutene resin coating or the film of substrate surface.
In addition, the application of benzocyclobutane olefine resin provided by the present invention in the preparation microelectronic packaging material also belongs to protection scope of the present invention.
Silicon-containing benzocyclobutene resin provided by the invention; Be to generate through being heating and curing by the end capped siloxanyl monomers of benzocyclobutene; Make and contain a large amount of benzene lateral groups groups or fluorine-containing benzene lateral group group in this silicon-containing benzocyclobutene resin, thereby have higher thermotolerance, lower water-intake rate (being lower than 0.20%) and lower specific inductivity (being lower than 2.70) and dielectric loss and (be lower than 3.3 * 10
-4) wait excellent properties.The compound ultraviolet curable resin that forms of this resin and photosensitivity auxiliary agent; After ultraviolet exposure, development, curing, can form high-resolution photoetching pattern; The layer insulation film, the multimedia messages carrier that can be applicable to the microelectronics Packaging field with insulation film, liquid-crystal display planarization film, nonlinear optical material and high performance adhesive etc., have important application prospects with film, microelectromechanical-systems (MEMS).
Embodiment
Embodiment 1, preparation 1,3-dimethyl--1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-phenylbenzene sily oxide
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 40 grams 1; 3-dimethyl--1; 3-divinyl-1; 3-phenylbenzene sily oxide, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 69 grams (productive rate 88%).
1H?NMR(300MHz，DMSO-d
6，δ)：7.59-7.61(d，4H)，7.38-7.41(m，6H)，7.21-7.23(d，4H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.11(s，8H)，0.49(s，6H).
Mass spectrum: 514 (molecular ion peak, intensity 85%);
Ultimate analysis: calculated value C, 79.32%; H, 6.66%; Measured value: C, 79.12%; H, 6.75%.
Embodiment 2, preparation 1,5-dimethyl--1,5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,5-phenylbenzene-3,3-phenylbenzene trisiloxanes
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 69 grams 1; 5-dimethyl--1; 5-divinyl-1; 5-phenylbenzene-3,3-phenylbenzene trisiloxanes, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 83 grams (productive rate 86%).
1H?NMR(300MHz，DMSO-d
6，δ)：7.55-7.56(d，4H)，7.51-7.53(d，4H)，7.28-7.45(m，12H)，7.06-7.08(d，2H)，7.02(s，2H)，6.97-6.99(d，2H)，6.88-6.92(d，2H)，6.38-6.42(d，2H)，3.08(s，8H)，0.41(s，6H).
Mass spectrum: 712 (molecular ion peak, intensity 55%);
Ultimate analysis: calculated value C, 77.48%; H, 6.22%; Measured value: C, 77.32%; H, 6.31%.
Embodiment 3, preparation 1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-tetraphenyl sily oxide
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 58 grams 1; 3-divinyl-1; 3-tetraphenyl sily oxide, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 74 grams (productive rate 85%).
1H?NMR(300MHz，CDCl
3-d，δ)：7.59-7.61(d，8H)，7.38-7.41(m，12H)，7.21-7.23(d，4H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.11(s，8H).
Mass spectrum: 638 (molecular ion peak, intensity 82%);
Ultimate analysis: calculated value C, 82.72%; H, 5.99%; Measured value: C, 82.64%; H, 5.75%.
Embodiment 4, preparation 1,3-dimethyl--1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-two (3 '-trifluoromethyl) sily oxide
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 60 grams 1; 3-dimethyl--1; 3-divinyl-1; 3-two (3 '-trifluoromethyl) sily oxide, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 72 grams (productive rate 81%).
1H?NMR(300MHz，DMSO-d
6，δ)：7.79(s，2H)，7.69-7.71(d，2H)，7.61-7.63(d，2H)，7.44-7.48(t，2H)，7.21-7.23(d，2H)，7.13-7.15(s，2H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.11(s，8H)，0.54(s，6H).
Mass spectrum: 650 (molecular ion peak, intensity 54%);
Ultimate analysis: calculated value C, 66.44%; H, 4.96%; Measured value: C, 66.64%; H, 4.75%.
Embodiment 5, preparation 1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-four (3 '-trifluoromethyl) sily oxide
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 95 grams 1; 3-divinyl-1; 3-four (3 '-trifluoromethyl) sily oxide, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 98 grams (productive rate 79%).
1H?NMR(300MHz，DMSO-d
6，δ)：7.79(s，4H)，7.69-7.71(d，4H)，7.61-7.63(4，2H)，7.44-7.48(t，4H)，7.21-7.23(d，2H)，7.13-7.15(s，2H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.11(s，8H).
Mass spectrum: 910 (molecular ion peak, intensity 34%);
Ultimate analysis: calculated value C, 63.29%; H, 3.76%; Measured value: C, 63.34%; H, 3.65%.
Embodiment 6, preparation 1,5-dimethyl--1,5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,5-two (3 '-trifluoromethyl)-3,3-phenylbenzene trisiloxanes
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 86 grams 1; 5-dimethyl--1; 5-divinyl-1; 5-two (3 '-trifluoromethyl)-3,3-phenylbenzene trisiloxanes, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 96 grams (productive rate 83%).
1H?NMR(300MHz，DMSO-d
6，δ)：7.79(s，4H)，7.69-7.71(d，4H)，7.52-7.66(m，12H)，7.44-7.48(t，4H)，7.21-7.23(d，2H)，7.13-7.15(s，2H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.11(s，8H).
Mass spectrum: 848 (molecular ion peak, intensity 56%);
Ultimate analysis: calculated value C, 67.91%; H, 4.99%; Measured value: C, 67.84%; H, 4.85%.
Embodiment 7, preparation 1,5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,5-four (3 '-trifluoromethyl)-3,3-phenylbenzene trisiloxanes
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 121 grams 1; 5-divinyl-1; 5-four (3 '-trifluoromethyl)-3; 3-phenylbenzene trisiloxanes, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 131 grams (productive rate 87%).
1H?NMR(300MHz，DMSO-d
6，δ)：7.79(s，2H)，7.69-7.71(d，2H)，7.52-7.66(m，12H)，7.44-7.48(t，2H)，7.21-7.23(d，2H)，7.13-7.15(s，2H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.11(s，8H)，0.54(s，6H).
Mass spectrum: 1108 (molecular ion peak, intensity 36%);
Ultimate analysis: calculated value C, 64.97%; H, 4.01%; Measured value: C, 64.84%; H, 4.05%.
Embodiment 8, preparation 1,3-dimethyl--1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-two (3 ' 5 '-two trifluoromethyls) sily oxide
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 78 grams 1; 3-dimethyl--1; 3-divinyl-1; 3-two (3 ' 5 '-two trifluoromethyls) sily oxide, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 81 grams (productive rate 76%).
1H?NMR(300MHz，DMSO-d
6，δ)：8.39(s，2H)，8.18(s，4H)，7.21-7.23(d，2H)，7.13-7.15(s，2H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.16(s，8H)，0.48(s，6H).
Mass spectrum: 786 (molecular ion peak, intensity 64%);
Ultimate analysis: calculated value C, 58.01%; H, 3.84%; Measured value: C, 58.14%; H, 3.89%.
Embodiment 9, preparation 1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-four (3 ' 5 '-two trifluoromethyls) sily oxide
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 132 grams 1; 3-divinyl-1; 3-four (3 ' 5 '-two trifluoromethyls) sily oxide, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 139 grams (productive rate 86%).
1H?NMR(300MHz，DMSO-d
6，δ)：8.39(s，4H)，8.18(s，8H)，7.21-7.23(d，2H)，7.13-7.15(s，2H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.13(s，8H).
Mass spectrum: 1182 (molecular ion peak, intensity 74%);
Ultimate analysis: calculated value C, 52.81%; H, 2.56%; Measured value: C, 52.74%; H, 2.63%.
Embodiment 10, preparation 1,5-dimethyl--1,5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,5-two (3 ' 5 '-two trifluoromethyls)-3,3-phenylbenzene trisiloxanes
In the flask that TM, nitrogen inlet and outlet, condensing surface and whisking appliance are housed, add 50 gram 4-bromobenzenes and cyclobutene, 105 grams 1; 5-dimethyl--1; 5-divinyl-1; 5-two (3 ' 5 '-two trifluoromethyls)-3,3-phenylbenzene trisiloxanes, 0.61 gram acid chloride, 3.32 gram triphenylphosphines, 48 gram triethylamine and 300 milliliters of acetonitriles stir under nitrogen protection and make reaction mixture formation homogeneous phase solution.Then, heating rises between 90～100 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 25 hours.After reacting completely, be cooled to room temperature; In reaction solution, add 1000 gram deionized waters, remove water after the liquid layering to be mixed; Organic phase is diluted with 500 milliliters of methylene dichloride, uses the washing of 5 * 500 ml deionized water to neutral again; Organic phase is used anhydrous magnesium sulfate drying; Low boiling point organic solvent is removed in distillation, passes through the column chromatography sharp separation with sherwood oil and ETHYLE ACETATE mixed solution as eluent again, and underpressure distillation obtains heavy-gravity transparent liquid product after removing eluent, and weight is 116 grams (productive rate 85%)
1H?NMR(300MHz，DMSO-d
6，δ)：8.39(s，2H)，8.18(s，4H)，7.52-7.66(m，10H)，7.21-7.23(d，2H)，7.13-7.15(s，2H)，7.02-7.04(d，2H)，6.96-7.01(d，2H)，6.51-6.55(d，2H)，3.11(s，8H)，0.52(s，6H).
Mass spectrum: 984 (molecular ion peak, intensity 26%);
Ultimate analysis: calculated value C, 60.96%; H, 4.09%; Measured value: C, 60.88%; H, 4.15%.
Embodiment 11, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 1 prepare 1,3-dimethyl--1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 3-phenylbenzene sily oxide adds in the mould; Vacuum defoamation 5～30min under 80～120 ℃ of conditions, in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under nitrogen or the argon gas condition; 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 12, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 1 prepare 1; 3-dimethyl--1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; Trimethylbenzene between 3-phenylbenzene sily oxide and 60 grams, nitrogen protection stir fast down and make reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 33.5 hours, and soltion viscosity increases to 350cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 16 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is 2.7 * 10
3, Mw is 125 * 10
3, molecular weight distribution mw/mn is 46.3, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 13, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 2 prepare 1,5-dimethyl--1,5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 5-phenylbenzene-3,3-phenylbenzene trisiloxanes add in the mould, vacuum defoamation 5～30min under 80～120 ℃ of conditions; Heated 1 hour in 100 ℃ under nitrogen or the argon gas condition; 150 ℃ were heated 1 hour, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 14, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 2 prepare 1; 5-dimethyl--1; 5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 5-phenylbenzene-3, trimethylbenzene between 3-phenylbenzene trisiloxanes and 60 grams, nitrogen protection is stirred fast down and is made reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 76.5 hours, and soltion viscosity increases to 520cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 16 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is 3.7 * 10
3, Mw is 132 * 10
3, molecular weight distribution mw/mn is 35.7, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 15, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 3 prepare 1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-tetraphenyl sily oxide add in the mould, vacuum defoamation 5～30min under 80～120 ℃ of conditions; Heated 1 hour in 100 ℃ under nitrogen or the argon gas condition; 150 ℃ were heated 1 hour, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 16, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 3 prepare 1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; Trimethylbenzene between 3-tetraphenyl sily oxide and 60 grams, nitrogen protection stir fast down and make reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 22.5 hours, and soltion viscosity increases to 430cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 15.2 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is .2 * 10
3, Mw is 72 * 10
3, molecular weight distribution mw/mn is 32.7, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 17, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 4 prepare 1,3-dimethyl--1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 3-two (3 '-trifluoromethyl) sily oxide adds in the mould; Vacuum defoamation 5～30min under 80～120 ℃ of conditions, in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under nitrogen or the argon gas condition; 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 18, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 4 prepare 1; 3-dimethyl--1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; Trimethylbenzene between 3-two (3 '-trifluoromethyl) sily oxide and 60 grams, nitrogen protection stir fast down and make reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 26.5 hours, and soltion viscosity increases to 395cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 16.4 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is .2 * 10
3, Mw is 72 * 10
3, molecular weight distribution mw/mn is 2.8 * 10
3, Mw is 83 * 10
3, molecular weight distribution mw/mn is 29.6, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 19, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 5 prepare 1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-four (3 '-trifluoromethyl) sily oxide add in the mould, vacuum defoamation 5～30min under 80～120 ℃ of conditions; Heated 1 hour in 100 ℃ under nitrogen or the argon gas condition; 150 ℃ were heated 1 hour, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 20, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 5 prepare 1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; Trimethylbenzene between 3-four (3 '-trifluoromethyl) sily oxide and 60 grams, nitrogen protection stir fast down and make reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 23.5 hours, and soltion viscosity increases to 365cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 15.2 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is 2.3 * 10
3, Mw is 78 * 10
3, molecular weight distribution mw/mn is 33.9, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 21, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 6 prepare 1,5-dimethyl--1,5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 5-two (3 '-trifluoromethyl)-3,3-phenylbenzene trisiloxanes add in the mould, vacuum defoamation 5～30min under 80～120 ℃ of conditions; Heated 1 hour in 100 ℃ under nitrogen or the argon gas condition; 150 ℃ were heated 1 hour, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 22, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 6 prepare 1; 5-dimethyl--1; 5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 5-two (3 '-trifluoromethyl)-3, trimethylbenzene between 3-phenylbenzene trisiloxanes and 60 grams, nitrogen protection is stirred fast down and is made reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 79.3 hours, and soltion viscosity increases to 538cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 17.2 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is 4.3 * 10
3, Mw is 128 * 10
3, molecular weight distribution mw/mn is 29.8, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 23, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 7 prepare 1,5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,5-four (3 '-trifluoromethyl)-3; 3-phenylbenzene trisiloxanes adds in the mould; Vacuum defoamation 5～30min under 80～120 ℃ of conditions, in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under nitrogen or the argon gas condition; 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 24, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 7 prepare 1; 5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 5-four (3 '-trifluoromethyl)-3; 3-phenylbenzene trisiloxanes and 60 grams are asked trimethylbenzene, and nitrogen protection is stirred fast down and made reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 76.5 hours, and soltion viscosity increases to 588cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 17.7 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is 4.2 * 10
3, Mw is 133 * 10
3, molecular weight distribution mw/mn is 31.7, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 25, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 8 prepare 1,3-dimethyl--1,3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 3-two (3 ' 5 '-two trifluoromethyls) sily oxide adds in the mould; Vacuum defoamation 5～30min under 80～120 ℃ of conditions, in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under nitrogen or the argon gas condition; 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 26, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 8 prepare 1; 3-dimethyl--1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; Trimethylbenzene between 3-two (3 ' 5 '-two trifluoromethyls) sily oxide and 60 grams, nitrogen protection stir fast down and make reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 28.4 hours, and soltion viscosity increases to 387cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 16.5 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is 2.0 * 10
3, Mw is 73 * 10
3, molecular weight distribution mw/mn is 36.5, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 27, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 9 prepare 1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1,3-four (3 ' 5 '-two trifluoromethyls) sily oxide add in the mould, vacuum defoamation 5～30min under 80～120 ℃ of conditions; Heated 1 hour in 100 ℃ under nitrogen or the argon gas condition; 150 ℃ were heated 1 hour, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 28, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 9 prepare 1; 3-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; Trimethylbenzene between 3-four (3 ' 5 '-two trifluoromethyls) sily oxide and 60 grams, nitrogen protection stir fast down and make reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 18.1 hours, and soltion viscosity increases to 288cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 15.5 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is 1.2 * 10
3, Mw is 33 * 10
3, molecular weight distribution mw/mn is 27.5, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
Embodiment 29, preparation silicon-containing benzocyclobutene resin
With 20 the gram by embodiment 10 prepare 1,5-dimethyl--1,5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 5-two (3 ' 5 '-two trifluoromethyls)-3,3-phenylbenzene trisiloxanes add in the mould, vacuum defoamation 5～30min under 80～120 ℃ of conditions; Heated 1 hour in 100 ℃ under nitrogen or the argon gas condition; 150 ℃ were heated 1 hour, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, the demoulding obtains completely crued benzocyclobutene resin-cast body.
The electrical property of this silicon-containing benzocyclobutene resin pour mass and optical property etc. are seen table 1.
Embodiment 30, preparation silicon-containing benzocyclobutene resin
In TM, nitrogen inlet and outlet, condensing surface and churned mechanically there-necked flask are housed, add 20 grams by embodiment 10 prepare 1; 5-dimethyl--1; 5-two [2 '-(4 '-benzocyclobutane thiazolinyl)] vinyl-1; 5-two (3 ' 5 '-two trifluoromethyls)-3, trimethylbenzene between 3-phenylbenzene trisiloxanes and 60 grams, nitrogen protection is stirred fast down and is made reaction mixture form homogeneous phase solution.Then, heating rises between 165～168 ℃ reacting liquid temperature, and solution is reflux state, stirring reaction 72.3 hours, and soltion viscosity increases to 415cPs, stops heating, is cooled to room temperature; It is added drop-wise in the Virahol of 800 milliliters of reflux, continue refluxed 30 minutes～1 hour after dripping again, stop heating, be cooled to the resin that suction filtration after the room temperature obtains white granular, 80 ℃ of vacuum-dryings obtain 15.8 gram B-stage resin after 10 hours.The Mn of this resin of gel permeation chromatography GPC test is 3.8 * 10
3, Mw is 117 * 10
3, molecular weight distribution mw/mn is 30.8, wherein is standard with vinylbenzene, toluene is eluent.
Claim that 10 these B-stage resin of gram are dissolved in 30 grams 1,3, in the trimethylbenzene, treat that solid all dissolves after-filtration between 5-, obtain B-stage resin solution.It is coated on the sheet glass, and in 100 ℃ of heating 1 hour, 150 ℃ were heated 1 hour under the condition of nitrogen gas, and 210 ℃ were heated 1 hour, and 250 ℃ were heated 1 hour; Cool to then below 100 ℃, peel off from substrate surface and obtain completely crued benzocyclobutene resin film.
The electrical property of this silicon-containing benzocyclobutene resin film and optical property etc. are seen table 1.
The performance characterization of table 1 silicon-containing benzocyclobutene resin
Claims (20)
1. a silicon-containing benzocyclobutene monomer has the general structure shown in the formula II;
Wherein, in the said formula II general structure, A, B, C, D, E, F are one or more in Wasserstoffatoms, fluorine atom, methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, the butyl; R
1Be methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, butyl phenyl, trifluoromethyl or 3,5-two trifluoromethyls; N is 0-10.
2. a method for preparing the said compound of claim 1 is that bi-vinyl siloxanes shown in 4-bromobenzene and cyclobutene and the formula III general structure is dissolved in the organic solvent reacting by heating under catalyst action;
(formula III)
Wherein, in the said formula III general structure, A, B, C, D, E, F are one or more in Wasserstoffatoms, fluorine atom, methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl or the butyl; R
1Be methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, butyl phenyl, trifluoromethyl or 3,5-two trifluoromethyls; N is 0-10.
3. method according to claim 2 is characterized in that: the mol ratio of said 4-bromobenzene and cyclobutene and said bi-vinyl siloxanes is 0.5-2.
4. method according to claim 3 is characterized in that: the mol ratio of said 4-bromobenzene and cyclobutene and said bi-vinyl siloxanes is 0.8-1.2.
5. according to claim 2 or 3 described methods, it is characterized in that: said catalyzer is sugar of lead, acid chloride, Palladous chloride, triphenylphosphine, three-(o-methyl-phenyl-) phosphine, three-(aminomethyl phenyl) phosphine or three-(p-methylphenyl) phosphine and the mixture that mixes by arbitrary proportion thereof.
6. according to claim 2 or 3 described methods; It is characterized in that: said organic solvent is THF, ether, N; Dinethylformamide, DMAC N,N, acetonitrile, diethylamine, Trimethylamine 99, triethylamine, tripropyl amine, Tri N-Propyl Amine or toluene and the mixture that mixes by arbitrary proportion thereof.
7. according to claim 2 or 3 described methods, it is characterized in that: said temperature of reaction is 5-200 ℃, and the said reaction times is 1-48 hour.
8. method according to claim 7 is characterized in that: said temperature of reaction is 5-120 ℃; The said reaction times is 12-24 hour.
9. a silicon-containing benzocyclobutene resin has general structure shown in the formula I;
Wherein, A, B, C, D, E, F are one or more in Wasserstoffatoms, fluorine atom, methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl or the butyl; R
1Be methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, butyl phenyl, trifluoromethyl or 3,5-two trifluoromethyls; N=0-10.
10. a silicon-containing benzocyclobutene resin has general structure shown in the formula I;
Wherein, A, B, C, D, E, F and R
1Be followed successively by Wasserstoffatoms, fluorine atom, trifluoromethyl, methyl, phenyl, trifluoromethyl, 3,5-two trifluoromethyls; N=0-2.
11. a method for preparing the said silicon-containing benzocyclobutene resin of claim 9 is that heat temperature raising is cooled to below 100 ℃ after 100-300 ℃ again with after the vacuum defoamation of silicon-containing benzocyclobutene monomer shown in the formula II;
Wherein, in the said formula II general structure, A, B, C, D, E, F are one or more in Wasserstoffatoms, fluorine atom, methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, the butyl; R
1Be methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, butyl phenyl, trifluoromethyl or 3,5-two trifluoromethyls; N is 1.
12. method according to claim 11 is characterized in that: the temperature of said vacuum defoamation is 80-120 ℃.
13. according to claim 11 or 12 described methods, it is characterized in that: the said deaeration time is 5-30min.
14. a method for preparing the said silicon-containing benzocyclobutene resin of claim 9 may further comprise the steps:
1) silicon-containing benzocyclobutene monomer shown in the formula II is dissolved in the organic solvent; Obtain the monomeric solution of silicon-containing benzocyclobutene, be stirred and heated to 160-180 ℃, solution backflow 6-200 hour; Be cooled to room temperature; The monomeric solution of said silicon-containing benzocyclobutene is scattered in the alcoholic solvent, and collecting precipitation obtains partly solidified B-stage benzocyclobutane olefine resin;
2) with said partly solidified B-stage benzocyclobutene resin dissolves in organic solvent; Carry out spin coating after being made into the solution that the quality percentage composition is the 5-60% solid content; Afterwards with said benzocyclobutane olefine resin heat temperature raising to 100-300 ℃, solidified 1-20 hour, be cooled to below 100 ℃;
Wherein, in the said formula II general structure, A, B, C, D, E, F are one or more in Wasserstoffatoms, fluorine atom, methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, the butyl; R
1Be methyl, trifluoromethyl, ethyl, propyl group, sec.-propyl, butyl phenyl, trifluoromethyl or 3,5-two trifluoromethyls; N is 1.
15. method according to claim 14 is characterized in that: said step 1) and step 2) in the monomeric solid content of silicon-containing benzocyclobutene be 10～60%, said percentage composition is the quality percentage composition.
16. according to claim 14 or 15 described methods; It is characterized in that: said organic solvent is toluene, YLENE, trimethylbenzene, N; Dinethylformamide, DMAC N,N or N-Methyl pyrrolidone and the mixture that mixes by arbitrary proportion thereof.
17. method according to claim 16 is characterized in that: said organic solvent is YLENE or a trimethylbenzene and the mixture that mixes by arbitrary proportion thereof.
18. according to claim 14 or 15 described methods, it is characterized in that: said alcoholic solvent is C
1-C
10A kind of or its mixture that mixes by arbitrary proportion in the saturated fatty alcohol.
19. method according to claim 18 is characterized in that: said alcoholic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, the trimethyl carbinol or tertiary amyl alcohol and the mixture that mixes by arbitrary proportion thereof.
20. claim 9 or 10 described benzocyclobutane olefine resins are in the application of preparation microelectronic packaging material.
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| CN2007103039412A CN101463042B (en) | 2007-12-21 | 2007-12-21 | Silicon-containing benzocyclobutene resin, intermediate thereof and preparation of the resin and intermediate |
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| CN102520584B (en) * | 2011-09-13 | 2014-05-07 | 复旦大学 | Photosensitive benzocyclobutene resin compound and preparation method thereof as well as patterning method thereof |
| WO2016070434A1 (en) * | 2014-11-07 | 2016-05-12 | 中国科学院上海有机化学研究所 | Organosiloxane containing benzocyclobutene group, and preparation and use thereof |
| CN111909192B (en) * | 2020-08-13 | 2022-06-21 | 中国科学院上海有机化学研究所 | Siloxane with low dielectric constant and loss at high frequency, preparation method and application thereof |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5882836A (en) * | 1993-04-29 | 1999-03-16 | The Dow Chemical Company | Photocurable formulation containing a partially polymerized divinylsiloxane linked bisbenzocyclobutene resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5882836A (en) * | 1993-04-29 | 1999-03-16 | The Dow Chemical Company | Photocurable formulation containing a partially polymerized divinylsiloxane linked bisbenzocyclobutene resin |
Non-Patent Citations (2)
| Title |
|---|
| R. WAYNE JOHNSON et al..Benzocyclobutene Interlayer Dielectrics for Thin Film Multichip Modules.《IEEE TRANSACTIONS ON COMPONENTS, HYBRIDS, AND MANUFACTURING TECHNOLOGY》.1990,第13卷(第2期),第347-352页. * |
| 左小彪等.新型含硅苯并环丁烯树脂的合成与性能研究.《2007年全国高分子学术论文报告会》.2007,A-P-057. * |
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