CN1880322A - Epoxy compound comprising silicone grease and their application and preparation process - Google Patents
Epoxy compound comprising silicone grease and their application and preparation process Download PDFInfo
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- CN1880322A CN1880322A CN 200510076837 CN200510076837A CN1880322A CN 1880322 A CN1880322 A CN 1880322A CN 200510076837 CN200510076837 CN 200510076837 CN 200510076837 A CN200510076837 A CN 200510076837A CN 1880322 A CN1880322 A CN 1880322A
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Abstract
This invention discloses a silicone grease epoxy compound and method for making same and application. The structural formula of the compound is indicated in formula(I), wherein: k is 0 or 1; m is an integer between 3 and 6; n is an integer between 1 and 9. This invented silicone grease epoxy compound has a double-functional-group structure, and definite chemical molecular structure and molecular weight. Thermosetting epoxy resin formed by hot-set reaction of this silicone grease epoxy compound and hardening agent has a low dielectric constant, dielectric loss and water(damp) absorption ratio, and has an important application value in high-tech field like microelectron packing.
Description
Technical field
The present invention relates to a kind of siliceous alicyclic epoxide compound and preparation method thereof and application.
Background technology
Cycloaliphatic epoxy resin is widely used in the electric apparatus insulating material of outdoor UV resistant because of its good synthetic chemistry, physics and mechanical property.Along with deepening continuously to its research and development; the kind of cycloaliphatic epoxy resin is more and more; range of application is more extensive, all has important use at aspects such as paint, coating, printing ink, High-Voltage Electrical Appliances insulation, reactive diluent, acid cleavage agent, electronic devices and components encapsulating compound, printed circuit board (PCB) supercoat and is worth.Along with the fast development of microelectronic device and super large-scale integration towards high-performance, multi-functional, high-density, small size, lightening direction, microelectronic packaging technology also from traditional dual-in-line type (DIP) and four limits lead-in wire platypelloid type (QFP), develops towards flip-chip-ball grid array (FC-PBGA), chip scale encapsulation (CSP), multi-chip module (MCM) and higher packaging density and more complicated system in package (SiP) direction.The fast development of microelectronic packaging technology has also proposed more and more higher performance requriements to the Resins, epoxy as important packaged material, mainly comprises: 1) high heat-resistant stability; 2) high mechanical strength and low modulus; 3) low-k and dielectric loss; 4) high electric insulation, and 5) low suction (tide) property etc.Microelectronic packaging material has low specific inductivity and dielectric loss can obviously reduce the loss that signal transmits in the plastic packaging circuit, reliability and work-ing life that low suction (tide) property can improve encapsulated circuit.
The silane segment is incorporated into weathering resistance, reduction surface tension, the increase gas permeability that can obviously improve material in the thermosetting epoxy resin material; Can also improve the snappiness of material, reduce modulus, reduce internal stress, improve resistance toheat, reduce suction (tide) property etc.Especially the dimethyl siloxane segment is incorporated in the polymer backbone of Resins, epoxy, but the rotation main polymer chain by siloxane bond is arranged in hydrophobic special construction, because dimethyl siloxane segmental dipole moment is little, have lower specific inductivity, dielectric loss and lower suction (tide) property simultaneously so contain dimethyl siloxane segmental polymer materials.
Wang has reported and has utilized the addition of silicon hydrogen that siliceous segment is introduced the method for the aliphatic epoxy resin that contains two keys, prepared polydimethylsiloxane acrylic acid epoxy ester film [Wang, W.Z.; Eur.Polym.J., 2003,39,1117-1123]; People such as Crivello introduce the cycloaliphatic epoxy resin that contains two keys by the addition of silicon hydrogen with siliceous segment, prepared obtained utilizing radiation curing contain silane segmental Resins, epoxy [Crivello, J.V., Lee, J.L., J.Polym.Sci.PartA, 1990,28,479.]; People such as Hsiue utilize silicon hydroxyl and epichlorohydrin reaction to obtain siliceous Resins, epoxy, at high temperature have higher carbon residue rate and oxygen index, and certain flame retardant efficiency [Hsiue, G.H are arranged; Wang W.J., CHANG, F.C.; J.Appl.Polym.Sci., 1999,
73, 123]; Organic diamine and epichlorohydrin reaction that people such as Shih and Ma will contain silane have obtained four-functional group epoxy resin [Shih, W.C.; Ma, C.; J.Appl.Polym.Sci., 1998,
69, 51], have low viscosity and mechanical strength preferably.
Summary of the invention
The purpose of this invention is to provide a kind of siliceous alicyclic epoxide compound and preparation method thereof.
Siliceous alicyclic epoxide compound provided by the present invention, its structural formula be suc as formula shown in the I,
Wherein, k is 0 or 1; M is the integer of 3-6; N is the integer of 1-9.
The preparation method of the siliceous alicyclic epoxide compound of the present invention, comprise the steps: 1) structural formula is carried out imidization reaction suc as formula containing of silane aliphatie diamine and structural formula such as the formula III two key acid anhydrides of containing of II, obtain the alicyclic diolefin of structural formula suc as formula IV; Wherein, k is 0 or 1; M is the integer of 3-6; N is the integer of 1-9.
(formula III)
(formula IV)
2), obtain described siliceous alicyclic epoxide compound with alicyclic diolefin of gained and organic peroxy acid-respons.
Wherein, step 1) is described contains the silane aliphatie diamine and the described mol ratio that contains two key acid anhydrides is 1: 2.0-2.5; Be preferably 1: 2.05.The solvent of imidization reaction is selected from one or more in tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, dioxane, toluene, dimethylbenzene and the N-Methyl pyrrolidone.
Imidization reaction comprises chemical imidization reaction or hot imidization reaction.
The condition of chemical imidization reaction is: be 1 with mol ratio earlier: 2.0-2.5 described contains the silane aliphatie diamine and describedly contained under two key acid anhydrides room temperatures reaction 10-20 hour, and the diacetyl oxide/pyridine mixing solutions that adds 5-10 times of diamines molar weight then at room temperature reacted 10-20 hour.Wherein, the volume ratio of diacetyl oxide and pyridine is 1 in diacetyl oxide/pyridine mixing solutions: 0.5-1.5.
The condition of hot imidization reaction is: be 1 with mol ratio earlier: 2.0-2.5 described contains the silane aliphatie diamine and describedly contained under two key acid anhydrides room temperatures reaction 10-20 hour, adds the isoquinoline 99.9 of catalytic amount then, is heated to 140-180 ℃ of back flow reaction 5-10 hour.
Step 2) mol ratio of described alicyclic diolefin and described organic peroxide acid is 1: 2-4 is preferably 1: 3; Temperature of reaction is 0-50 ℃, and the reaction times is 6-24 hour.Organic peroxide acid commonly used has Peracetic Acid, peroxide propynoic acid, benzoyl hydroperoxide, metachloroperbenzoic acid or a nitro benzoyl hydroperoxide etc.
The siliceous alicyclic epoxide compound preparation feedback of the present invention equation is as follows:
Another object of the present invention provides the siliceous PROPERTIES AND APPLICATION OF ALICYCLIC EPOXIDES of the present invention.
Siliceous alicyclic epoxide compound of the present invention has double-functional group, forms matrix material with other components such as solidifying agent etc., can be used for fields such as microelectronics Packaging.
Concrete, a kind of cured resin, contain following components by part by weight:
The siliceous alicyclic epoxide compound 80-100 of the present invention,
Solidifying agent 20-80,
Curing catalyst 0.3-1.0.
Wherein, solidifying agent is selected from one or more in 4-methyl hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, HHPA, tetrahydrophthalic anhydride and the methyl carbic anhydride.
Curing catalyst is selected from imidazoles, glyoxal ethyline, 2,4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1,3,5-triethyl-six hydrogen-S-triazine, 1,3,5-trimethylammonium-six hydrogen-S-triazine, 2,4,6-three (dimethylamine methyl) phenol, 1, one or more in 8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU), triphenylphosphine, triethyl phosphine, acetylacetone cobalt, ferric acetyl acetonade, acetylacetonate nickel, methyl ethyl diketone neodymium and the aluminium acetylacetonate.
The preparation process of this cured resin is: with the siliceous alicyclic epoxide compound of the present invention, solidifying agent, curing catalyst uniform mixing, pour in the mould then and be heating and curing, condition of cure is: 120-160 ℃ solidified 1-2 hour, 160-200 ℃ after fixing 2-6 hour; Cured article is slowly cooled to room temperature, obtain uniform and smooth, the no bubble in surface, flawless cured resin.
When in above-mentioned cured resin, adding following components by part by weight:
Preparing spherical SiO 2 filler 600-1000,
Silane coupling agent 1-5.
Can obtain a kind of solids epoxy plastic cement, this moment, selected solidifying agent can be one or more in HHPA and the tetrahydrophthalic anhydride.
When in above-mentioned cured resin, adding following components by part by weight:
Preparing spherical SiO 2 filler 200-400,
Silane coupling agent 1-5.
Can obtain a kind of liquid epoxy and seal material, this moment, selected solidifying agent can be one or more in 4-methyl hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride and the methyl carbic anhydride.
Siliceous alicyclic epoxide compound of the present invention also can prepare becomes conductive silver paste, and this epoxy conductive silver is starched, and contains the component of following weight:
The siliceous alicyclic epoxide compound 100 of the present invention,
Solidifying agent 20-60,
Curing catalyst 0.3-1.0,
Silver powder 100-400,
Silane coupling agent 1-5.
To can make after the said components Hybrid Heating.
Siliceous alicyclic epoxide compound of the present invention has the double-functional group structure, the molecular weight that has definite chemical molecular structure and determine, the thermosetting epoxy resin that forms after the thermofixation reaction with solidifying agent has lower specific inductivity, dielectric loss and lower suction (tide) rate, has important use and be worth in high-technology fields such as microelectronics Packaging.
Embodiment
Embodiment 1,
In the there-necked flask that nitrogen conduit, thermometer, prolong and magnetic agitation are housed, add the 100ml tetrahydrofuran (THF) successively, 10.0g diamines propyl group tetramethyl disiloxane.Feed nitrogen, stir and under room temperature, add the 13.0g tetrahydrophthalic anhydride after 10 minutes in batches, add in 10 minutes.At room temperature reacted 12 hours, and added 100ml diacetyl oxide/pyridine mixing solutions (volume ratio is 1: 1) then, at room temperature reacted again 12 hours.Concentrate and remove unnecessary solvent, in heavy-gravity solution, separate out yellow crystals, wash with sherwood oil and water logging successively, obtain faint yellow solid---siliceous alicyclic ring diolefin A.
Thermometer will be housed and the magnetic agitation there-necked flask places ice bath to cool off, add 100ml methylene dichloride and 10.0g metachloroperbenzoic acid, stir about dripped siliceous alicyclic ring diolefin A and the 30ml methylene dichloride mixed solution of 10.0g in 0 ℃ after 10 minutes, added in 2 hours, and continued reaction 10 hours in 0 ℃.Filter, filtrate is used 20%Na
2SO
3, 5%NaOH and deionized water be washed till neutrality, organic phase Na
2SO
4Dry.The white powder that obtains after concentrating obtains white solid with sherwood oil/methylene dichloride mixing solutions (volume ratio 2: 1) recrystallization---and siliceous epoxy compounds I (m=3 among the formula I, n=1, k=0).
The epoxy equivalent (weight) that resulting epoxy compounds I measures is a 275g/eq (theoretical value: 274g/eq); Its
112 hydrogen of chemical shift at the 0ppm place are the hydrogen on the silicon methyl among the H-NMR, 0.5ppm the hydrogen on the methylene radical of locating that 4 hydrogen are with silicon links to each other, 1.6ppm 4 hydrogen locating are the hydrogen on the propane intermediate sub methyl, 2.2-2.6ppm 8 hydrogen locating are the hydrogen on the methylene radical in the six-ring, 2.7ppm the hydrogen on the carbon that 4 hydrogen locating are oxirane rings, 3.2ppm the hydrogen on the carbon of locating that 4 hydrogen are with carbonyl links to each other, 3.5ppm the hydrogen on the methylene radical of locating that 4 hydrogen are with nitrogen links to each other shows that institute's synthetic compound structure is correct.
Embodiment 2,
In the there-necked flask that nitrogen conduit, thermometer, prolong and magnetic agitation are housed, add the 100ml N-Methyl pyrrolidone successively, 10g diamines propyl group tetramethyl disiloxane.Feed nitrogen, stir and under room temperature, add the 13.5g carbic anhydride after 10 minutes in batches, add in 10 minutes.After at room temperature reacting 12 hours, add 90ml diacetyl oxide/pyridine mixing solutions (volume ratio 1: 1), at room temperature reacted again 12 hours.Concentrate and remove unnecessary solvent, in heavy-gravity solution, separate out yellow crystals, wash with sherwood oil and water logging successively, obtain faint yellow solid---siliceous alicyclic ring diolefin B.
Thermometer will be housed and the magnetic agitation there-necked flask places ice bath to cool off, add 100ml methylene dichloride and 10.0g benzoyl hydroperoxide, stir about in 0 ℃ of siliceous alicyclic ring diolefin B and 40ml methylene dichloride mixed solution of dropping 10.0g, added after 10 minutes in 2 hours, continued reaction 10 hours in 0 ℃.Filter, filtrate is used 20%Na
2SO
3, 5%NaOH and deionized water be washed till neutrality, organic phase Na
2SO
4Dry.The white powder that obtains after concentrating obtains white solid with sherwood oil/methylene dichloride mixing solutions (volume ratio 2: 1) recrystallization---and siliceous epoxy compounds II (m=3 among the formula I, n=1, k=1).
The epoxy equivalent (weight) that resulting epoxy compounds II measures is a 288g/eq (theoretical value: 286g/eq); Its
112 hydrogen of chemical shift at the 0ppm place are the hydrogen on the silicon methyl among the H-NMR, 0.5ppm the hydrogen on the methylene radical of locating that 4 hydrogen are with silicon links to each other, 1.6-1.7ppm 8 hydrogen locating are the hydrogen on the methylene radical in propane intermediate sub methyl and the bridged ring, 2.2-2.6ppm 4 hydrogen locating are the hydrogen on the methylene radical in the six-ring, 2.7ppm the hydrogen on the carbon that 4 hydrogen locating are oxirane rings, 3.2ppm the hydrogen on the carbon of locating that 4 hydrogen are with carbonyl links to each other, 3.5ppm the hydrogen on the methylene radical of locating that 4 hydrogen are with nitrogen links to each other shows that institute's synthetic compound structure is correct.
Embodiment 3,
In the there-necked flask that nitrogen conduit, thermometer, prolong and magnetic agitation are housed, add the 80ml N,N-DIMETHYLACETAMIDE successively, 10.0gl, 6-diamines propyl group ten dimethyl six siloxanes.Feed nitrogen, stir and under room temperature, add the 6.0g tetrahydrophthalic anhydride after 10 minutes in batches, add in 10 minutes.At room temperature reacted 12 hours.Add 80ml diacetyl oxide/pyridine mixing solutions (volume ratio 1: 1), at room temperature reacted again 12 hours.Concentrate and remove unnecessary solvent, in heavy-gravity solution, separate out yellow crystals, wash with sherwood oil and water logging successively, obtain the siliceous alicyclic ring diolefin C of faint yellow solid.
Thermometer will be housed and the magnetic agitation there-necked flask places ice bath to cool off, add 90ml methylene dichloride and 8.0g Peracetic Acid, stir about dripped siliceous alicyclic ring diolefin C and the 30ml methylene dichloride mixed solution of 10.0g in room temperature after 10 minutes, added in 2 hours, continued reaction 10 hours in 50 ℃.Filter, filtrate is used 20%Na
2SO
3, 5%NaOH and deionized water be washed till neutrality, organic phase Na
2SO
4Dry.The white powder that obtains after concentrating with sherwood oil/methylene dichloride mixing solutions (volume ratio 2: 1) recrystallization obtain the siliceous epoxy compounds III of white solid (m=3 among the formula I, n=5, k=0).
The epoxy equivalent (weight) that resulting epoxy compounds III measures is a 425g/eq (theoretical value: 422g/eq); Its
136 hydrogen of chemical shift at the 0ppm place are the hydrogen on the silicon methyl among the H-NMR, 0.5ppm the hydrogen on the methylene radical of locating that 4 hydrogen are with silicon links to each other, 1.6ppm 4 hydrogen locating are the hydrogen on the propane intermediate sub methyl, 2.2-2.6ppm 8 hydrogen locating are the hydrogen on the methylene radical in the six-ring, 2.7ppm the hydrogen on the carbon that 4 hydrogen locating are oxirane rings, 3.2ppm the hydrogen on the carbon of locating that 4 hydrogen are with carbonyl links to each other, 3.5ppm the hydrogen on the methylene radical of locating that 4 hydrogen are with nitrogen links to each other shows that institute's synthetic compound structure is correct.
Embodiment 4,
Add 20ml toluene and 80ml N-Methyl pyrrolidone successively in the there-necked flask that nitrogen conduit, thermometer, prolong and magnetic agitation are housed, 10.0g 1,6-diamines propyl group ten dimethyl six siloxanes.Feed nitrogen, stir and under room temperature, add the 6.0g carbic anhydride after 10 minutes in batches, add in 10 minutes.At room temperature reacted 12 hours.Add several isoquinoline 99.9, be warmed up to 160 ℃ and reacted again 6 hours.Concentrate and remove unnecessary solvent, in heavy-gravity solution, separate out yellow crystals, wash with sherwood oil and water logging successively, obtain the siliceous alicyclic ring diolefin D of faint yellow solid.
Thermometer will be housed and the magnetic agitation there-necked flask places ice bath to cool off, add nitro benzoyl hydroperoxide between 80ml methylene dichloride and 6.0g, stir about dripped siliceous alicyclic ring diolefin D and the 30ml methylene dichloride mixed solution of 10.0g in 0 ℃ after 10 minutes, added in 2 hours, and continued reaction 10 hours in 0 ℃.Filter, filtrate is used 20%Na
2SO
3, 5%NaOH and deionized water be washed till neutrality, organic phase Na
2SO
4Dry.The white powder that obtains after concentrating with sherwood oil/methylene dichloride mixing solutions (volume ratio 2: 1) recrystallization obtain the siliceous epoxy compounds IV of white solid (m=3 among the formula I, n=5, k=1).
The epoxy equivalent (weight) that resulting epoxy compounds IV measures is a 438g/eq (theoretical value: 434g/eq); Its
136 hydrogen of chemical shift at the 0ppm place are the hydrogen on the silicon methyl among the H-NMR, 0.5ppm the hydrogen on the methylene radical of locating that 4 hydrogen are with silicon links to each other, 1.6-1.7ppm 8 hydrogen locating are the hydrogen on the methylene radical in propane intermediate sub methyl and the bridged ring, 2.2-2.6ppm 8 hydrogen locating are the hydrogen on the methylene radical in the six-ring, 2.7ppm the hydrogen on the carbon that 4 hydrogen locating are oxirane rings, 3.2ppm the hydrogen on the carbon of locating that 4 hydrogen are with carbonyl links to each other, 3.5ppm the hydrogen on the methylene radical of locating that 4 hydrogen are with nitrogen links to each other shows that institute's synthetic compound structure is correct.
Embodiment 5, preparation cured resin
Get the siliceous epoxy compounds I 10.0g of embodiment 1 preparation, 4-methyl hexahydrophthalic anhydride 5.0g, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.10g heats and stirs into homogeneous phase solution.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 160 ℃ solidified 2 hours, 190 ℃ of after fixing 2 hours.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.
Recording its volume specific resistance is 2.3 * 10
16Ω cm, 25 ℃ of specific inductivity when recording 1MHz are 3.2, adopting Q table method to measure its dielectric loss is 0.0024; This cured resin disk at room temperature soaked record water-intake rate 0.48% after 24 hours.
Embodiment 6, preparation cured resin
Get the siliceous epoxy compounds II 10.0g of embodiment 2 preparation, HHPA 4.5g, glyoxal ethyline 0.05g heats and stirs into homogeneous phase solution.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 150 ℃ solidified 2 hours, 180 ℃ of after fixing 3 hours.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.
Recording its volume specific resistance is 3.3 * 10
16Ω cm, 25 ℃ of specific inductivity when recording 1MHz are 3.3, dielectric loss is 0.0048; This cured resin disk soaked at room temperature to record water-intake rate after 24 hours be 0.50%.
Embodiment 7, preparation cured resin
Get the siliceous epoxy compounds III 10.0g of embodiment 3 preparation, 4-methyl tetrahydro phthalic anhydride 3.2g, 1,8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU) 0.07g heats and stirs into homogeneous phase solution.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 140 ℃ solidified 2 hours, 190 ℃ of after fixing 2 hours.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.
Recording its volume specific resistance is 3.0 * 10
16Ω cm, 25 ℃ of specific inductivity when recording 1MHz are 3.1, dielectric loss is 0.0035; This cured resin disk soaked at room temperature to record water-intake rate after 24 hours be 0.48%.
Embodiment 8, preparation cured resin
Get the siliceous epoxy compounds IV 10.0g of embodiment 4 preparation, tetrahydrophthalic anhydride 2.8g, 2,4,6-three (dimethylamine methyl) phenol (DMP-30) 0.10g heats and stirs into homogeneous phase solution.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 160 ℃ solidified 2 hours, 200 ℃ of after fixing 3 hours.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.
Recording its volume specific resistance is 3.4 * 10
16Ω cm, 25 ℃ of specific inductivity when recording 1MHz are 3.2, dielectric loss is 0.0042; This cured resin disk soaked at room temperature to record water-intake rate after 24 hours be 0.50%.
Comparative Examples 1
Get ERL-4221 (Dow company) 10.0g, 4-methyl hexahydrophthalic anhydride 10.0g, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.10g heats and stirs into homogeneous phase solution.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 150 ℃ solidified 2 hours, and 180 ℃ solidified 4 hours.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.
Recording its volume specific resistance is 7.9 * 10
16Ω cm, 25 ℃ of specific inductivity when recording 1MHz are 3.6, dielectric loss is 0.0069; This cured resin disk soaked at room temperature to record water-intake rate after 24 hours be 0.54%.
Above result shows that the cured resin that is raw material with siliceous alicyclic epoxide compound of the present invention has the excellent comprehensive performance, can be applied in the microelectronics Packaging.
Embodiment 9, preparation solids epoxy plastic cement
Get the siliceous epoxy compounds I 10g of embodiment 1 preparation, tetrahydrophthalic anhydride 5g, glyoxal ethyline 0.5g, KH-560 silane coupling agent 0.5g, preparing spherical SiO 2 85g mixes and prepares the solids epoxy plastic cement.
140 ℃ of this solids epoxy plastic cement second-order transition temperatures, linear expansivity is 12ppm/ ℃, water-intake rate is 0.10%.
Embodiment 10, preparation solids epoxy plastic cement
Get the siliceous epoxy compounds I 10g of embodiment 1 preparation, HHPA 3g, 2-ethyl-4-methylimidazole 1.0g, KH-560 silane coupling agent 0.1g, preparing spherical SiO 2 65g mixes and prepares the solids epoxy plastic cement.
145 ℃ of this solids epoxy plastic cement second-order transition temperatures, linear expansivity is 14ppm/ ℃, water-intake rate is 0.11%.
Embodiment 11, preparation liquid epoxy are sealed material
Get the siliceous epoxy compounds I20g of embodiment 1 preparation, methyl hexahydrophthalic anhydride 10g, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.2g, KH-560 silane coupling agent 0.5g, preparing spherical SiO 2 70g mixes and prepares liquid epoxy and seal material.
This liquid epoxy is sealed 145 ℃ of material second-order transition temperatures, linear expansivity 25ppm/ ℃, water-intake rate 0.14%.
Embodiment 12, preparation liquid epoxy are sealed material
Get the siliceous epoxy compounds I20g of embodiment 1 preparation, methyl tetrahydro phthalic anhydride 6g, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.2g, KH-560 silane coupling agent 0.5g, preparing spherical SiO 2 50g mixes and prepares liquid epoxy and seal material.
This liquid epoxy is sealed 140 ℃ of material second-order transition temperatures, linear expansivity 27ppm/ ℃, water-intake rate 0.15%.
Embodiment 13, preparation epoxy conductive silver slurry
Get the siliceous epoxy compounds I20g of embodiment 1 preparation, methyl tetrahydro phthalic anhydride 4g, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.2g, KH-560 silane coupling agent 0.5g, silver powder 50g mixes and prepares epoxy conductive silver slurry.
140 ℃ of this epoxy conductive silver slurry second-order transition temperatures, thermal conductivity 97W/mK.
Claims (17)
1, a kind of siliceous alicyclic epoxide compound, its structural formula be suc as formula shown in the I,
(formula I)
Wherein, k is 0 or 1; M is the integer of 3-6; N is the integer of 1-9.
2, the preparation method of the described siliceous alicyclic epoxide compound of claim 1, comprise the steps: 1) structural formula is carried out imidization reaction suc as formula containing of silane aliphatie diamine and structural formula such as the formula III two key acid anhydrides of containing of II, obtain the alicyclic diolefin of structural formula suc as formula IV; Wherein, k is 0 or 1; M is the integer of 3-6; N is the integer of 1-9.
(formula II)
(formula III)
(formula IV)
2), obtain described siliceous alicyclic epoxide compound with alicyclic diolefin of gained and organic peroxy acid-respons.
3, preparation method according to claim 2 is characterized in that: describedly contain the silane aliphatie diamine and the described mol ratio that contains two key acid anhydrides is 1: 2.0-2.5; Be preferably 1: 2.05.
4, according to claim 2 or 3 described preparation methods, it is characterized in that: the solvent of described imidization reaction is selected from one or more in tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, dioxane, toluene, dimethylbenzene and the N-Methyl pyrrolidone.
5, preparation method according to claim 4 is characterized in that: described imidization reaction comprises chemical imidization reaction or hot imidization reaction.
6, preparation method according to claim 5, it is characterized in that: the condition of described chemical imidization reaction is: be 1 with mol ratio earlier: 2.0-2.5 described contains the silane aliphatie diamine and describedly contained under two key acid anhydrides room temperatures reaction 10-20 hour, and the diacetyl oxide/pyridine mixing solutions that adds 5-10 times of diamines molar weight then at room temperature reacted 10-20 hour.
7, preparation method according to claim 6 is characterized in that: the volume ratio of diacetyl oxide and pyridine is 1 in described diacetyl oxide/pyridine mixing solutions: 0.5-1.5.
8, preparation method according to claim 5, it is characterized in that: the condition of described hot imidization reaction is: mol ratio is 1: 2.0-2.5 described contains the silane aliphatie diamine and describedly contained under two key acid anhydrides room temperatures reaction 10-20 hour, the isoquinoline 99.9 that adds catalytic amount then was heated to 140-180 ℃ of back flow reaction 5-10 hour.
9, according to claim 2 or 3 described preparation methods, it is characterized in that: step 2) mol ratio of described alicyclic diolefin and described organic peroxide acid is 1: 2-4 is preferably 1: 3; Temperature of reaction is 0-50 ℃, and the reaction times is 6-24 hour.
10, according to claim 2 or 3 described preparation methods, it is characterized in that: described organic peroxide acid is Peracetic Acid, peroxide propynoic acid, benzoyl hydroperoxide, metachloroperbenzoic acid or a nitro benzoyl hydroperoxide.
11, a kind of cured resin, contain following components by part by weight:
The described siliceous alicyclic epoxide compound 80-100 of claim 1,
Solidifying agent 20-80,
Curing catalyst 0.3-1.0.
12, cured resin according to claim 11 is characterized in that: described cured resin also contains following components by part by weight:
Preparing spherical SiO 2 filler 600-1000,
Silane coupling agent 1-5.
13, cured resin according to claim 11 is characterized in that: described cured resin also contains following components by part by weight:
Preparing spherical SiO 2 filler 200-400,
Silane coupling agent 1-5.
14, according to claim 11 or 12 or 13 described cured resins, it is characterized in that: described solidifying agent is selected from one or more in 4-methyl hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, HHPA, tetrahydrophthalic anhydride and the methyl carbic anhydride.
15, according to claim 11 or 12 or 13 described cured resins, it is characterized in that: described curing catalyst is selected from imidazoles, glyoxal ethyline, 2, the 4-methylimidazole, 2-ethyl-4-methylimidazole, the 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1,3,5-triethyl-six hydrogen-S-triazine, 1,3,5-trimethylammonium-six hydrogen-S-triazine, 2,4,6-three (dimethylamine methyl) phenol, 1,8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU), triphenylphosphine, triethyl phosphine, acetylacetone cobalt, ferric acetyl acetonade, acetylacetonate nickel, in methyl ethyl diketone neodymium and the aluminium acetylacetonate one or more.
16, a kind of epoxy conductive silver is starched, and contains the component of following weight:
The described siliceous alicyclic epoxide compound 100 of claim 1,
Solidifying agent 20-60,
Curing catalyst 0.3-1,
Silver powder 100-400,
Silane coupling agent 1-5.
17, epoxy conductive silver slurry according to claim 16, it is characterized in that: described solidifying agent is selected from one or more in 4-methyl hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, HHPA, tetrahydrophthalic anhydride and the methyl carbic anhydride; Described curing catalyst is selected from imidazoles, glyoxal ethyline, 2, the 4-methylimidazole, 2-ethyl-4-methylimidazole, the 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1,3,5-triethyl-six hydrogen-S-triazine, 1,3,5-trimethylammonium-six hydrogen-S-triazine, 2,4,6-three (dimethylamine methyl) phenol, 1,8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU), triphenylphosphine, triethyl phosphine, acetylacetone cobalt, ferric acetyl acetonade, acetylacetonate nickel, in methyl ethyl diketone neodymium and the aluminium acetylacetonate one or more.
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| US20100258983A1 (en) * | 2007-11-07 | 2010-10-14 | Showa Denko K.K. | Epoxy group-containing organosiloxane compound, curable composition for transfer materials and method for forming micropattern using the composition |
| US8138296B2 (en) * | 2006-06-07 | 2012-03-20 | Showa Denko K.K. | Epoxy compounds and process for their production |
| CN103517948A (en) * | 2011-05-13 | 2014-01-15 | 日立化成株式会社 | Epoxy resin molding material for encapsulation and electronic component device |
| CN104755524A (en) * | 2012-11-09 | 2015-07-01 | 株式会社大赛璐 | Epoxy compound, production method therefor, and curable epoxy resin composition |
| CN114687246A (en) * | 2022-02-17 | 2022-07-01 | 固德电材系统（苏州）股份有限公司 | Epoxy-based silicone resin sizing agent, mica plate and preparation method and application thereof |
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| US5936059A (en) * | 1997-08-29 | 1999-08-10 | Jacam Chemical Partners, Ltd. | Epoxy corrosion inhibition systems including ethoxylated curing agents |
| CN1583816A (en) * | 2003-08-21 | 2005-02-23 | 中国科学院化学研究所 | Silicon containing organic amine epoxy resin curing agent |
| CN1271165C (en) * | 2003-09-03 | 2006-08-23 | 中国科学院化学研究所 | Liquid epoxy packaging material and its preparation method and application |
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| US8138296B2 (en) * | 2006-06-07 | 2012-03-20 | Showa Denko K.K. | Epoxy compounds and process for their production |
| US20100258983A1 (en) * | 2007-11-07 | 2010-10-14 | Showa Denko K.K. | Epoxy group-containing organosiloxane compound, curable composition for transfer materials and method for forming micropattern using the composition |
| US8604150B2 (en) * | 2007-11-07 | 2013-12-10 | Showa Denko K.K. | Epoxy group-containing organosiloxane compound, curable composition for transfer materials and method for forming micropattern using the composition |
| CN103517948A (en) * | 2011-05-13 | 2014-01-15 | 日立化成株式会社 | Epoxy resin molding material for encapsulation and electronic component device |
| CN104755524A (en) * | 2012-11-09 | 2015-07-01 | 株式会社大赛璐 | Epoxy compound, production method therefor, and curable epoxy resin composition |
| CN114687246A (en) * | 2022-02-17 | 2022-07-01 | 固德电材系统（苏州）股份有限公司 | Epoxy-based silicone resin sizing agent, mica plate and preparation method and application thereof |
| CN115197399A (en) * | 2022-07-12 | 2022-10-18 | 中山大学 | Preparation method and application of alicyclic epoxy polyimide |
| CN115197399B (en) * | 2022-07-12 | 2023-06-16 | 中山大学 | Preparation method and application of alicyclic epoxy polyimide |
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