CN102898648A - Chemical crosslinking-curable phenyl MDQ-type silicone resin and preparation method thereof - Google Patents
Chemical crosslinking-curable phenyl MDQ-type silicone resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of organic polymer chemistry and provides a chemical crosslinking-curable phenyl MDQ-type silicone resin and a preparation method thereof. The chemical crosslinking-curable phenyl MDQ-type silicone resin solves the problem that the existing MDQ-type silicone resin has a low refractive index and is not cured by a chemical crosslinking method, and improves optical and mechanical properties of a silicone resin-reinforced rubber-type packaging material. Hexamethyldisiloxane and 1,3-divinyltetramethyldisiloxane as blocking agents, methylphenyldiethoxysilane as a D chain unit source and tetraethoxysilane as a Q chain unit source undergo a co-hydrolytic condensation reaction in the presence of an ethanol aqueous solution as a reaction solvent, toluene as an extractant and hydrochloric acid as a catalyst to produce the chemical crosslinking-curable phenyl MDQ-type silicone resin. The chemical crosslinking-curable phenyl MDQ-type silicone resin improves mechanical properties of a MDQ-type silicone resin-reinforced rubber-type packaging material and improves optical properties of the rubber-type packaging material. The preparation method has mild reaction conditions, has simple processes and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the organic polymer chemical field, but a kind of chemically crosslinked phenyl MDQ type silicon resin and the synthetic method thereof of solidifying specifically.
Background technology
The organosilicon polymer of silicon hydrogen addition curing except the advantage with common organosilicon material, also have because of no coupling product in the sulfidization molding process generates, shrinking percentage is little and can deep layer vulcanization etc. characteristics, in the electronic apparatus encapsulation, have important use.But the organosilicon polymer cohesive energy density(CED) is little, and without the organosilicon polymer poor mechanical property of filler reinforcement, the performance index such as its tensile strength, elongation at break, tear strength and hardness can't satisfy the needs of packaged material.Vapor phase process or precipitated silica are the reinforced fillings of the most common and consumption maximum of organosilicon body material, but it is also very obvious for the silicon rubber thickening effect, cause compound viscosity to increase, and affect the course of processing and the practical ranges of silicon rubber.
Organosilicon encapsulating material should have before sulfidization molding than having behind low viscosity and the sulfidization molding the suitable physical strength, when packaged material during as the optical path material of photoelectric device, also should have optical property and the good anti-uv irradiation performances such as high transmission rate, specific refractory power, the specific refractory power size has determined the size of the packaging cirtical angle of total reflection, is the important factor of getting optical efficiency that affects photoelectric device.
The addition curable organosilicon encapsulating material of high refractive index is that the components such as filler, catalyst for addition reaction of hydrogen and silicon and inhibitor by the containing hydrogen silicone oil linking agent of the organosilicon body material of high refractive index, high refractive index, high refractive index consist of.Chinese invention patent CN101851333B and CN101289538B disclose the preparation method of high refractive index methyl and phenyl hydrogen-containing silicon oil linking agent, Chinese invention patent CN101475689B discloses the preparation method of high refractive index methyl phenyl vinyl polysiloxane, (the Xu Xiaoqiu such as Xu Xiaoqiu, Yang Xiongfa, Wu Chuan, come state's bridge, Jiang Jianxiong. the preparation and property research of LED gel-type packaged material base polymer. polymer material science and engineering journal, 2011,27(2): 129-132.) disclose specific refractory power between 1.45 ~ 1.52, the gel-type LED encapsulation matrix material preparation method of clear.Known as those skilled in the art, as the close encapsulation matrix material of specific refractory power or the linking agent of methyl phenyl vinyl polysiloxane, after solidifying, addition reaction of silicon with hydrogen can obtain respectively gel-type and the resin type packaged material of high refractive index with the containing hydrogen silicone oil of high refractive index.But gel-type packaged material bad mechanical property can only be as the interior protecting materials of photoelectric device; And resin type packaged material hardness is large, is typically used as lens material; During the high refractive index rubber-type packaged material of mechanical property between gel-type packaged material and resin type packaged material still is in and constantly improves, the key factor that affects the packaged material mechanical property is can participate in the reinforced filling molecule functional group's character and the content of chemical crosslink reaction, the optical properties such as the transmittance of packaged material, specific refractory power after the height of reinforced filling specific refractory power has then determined to solidify.
Except the mineral fillers such as silicon-dioxide, titanium dioxide, aluminium hydroxide, aluminum oxide, calcium carbonate, have the MQ resin of nucleocapsid structure and the reinforced filling that derivative also can be used as the organosilicon body material thereof, compare with mineral filler, MQ resin and derivative thereof not only give organosilicon polymer good mechanical property, and the adding of MQ resin for the organosilicon polymer viscosity influence much smaller than mineral filler, so the MQ resin has the function that other filler can not be substituted in the organosilicon encapsulating material system.The silicone resin of MDQ type is a kind of in the MQ silicone resin, and it is by single functionality silica chain link (R
1R
2R
3SiO
1/2, the M chain link), two functionality silica chain link (R
4R
5SiO
2/2, the D chain link) and four functionality silica chain link (SiO
4/2, the Q chain link) silicoorganic compound form through cohydrolysis-polycondensation.(the Li Yu such as Li Yu, Hu Xinsong, Lin Xiaodan, Ceng Xingrong: the MQ resin is studied add-on type RTV organic silicon potting adhesive reinforcing property. Chinese tackiness agent, 2010,19(11): 36-39.) hexamethyldisiloxane and tetramethyl divinyl disiloxane are joined HCl, in the mixing solutions that toluene and water etc. form, 70～80 ℃ mix, then in 60 min, drip simultaneously tetraethoxy and dimethyldiethoxysilane, continue reaction 60 min, standing demix when question response is complete, take off a layer mixed solution, to neutral, obtaining the vinyl massfraction behind the drying under reduced pressure is 2.6% with deionized water wash, M/Q be 0.6 or 0.7, D unit ratio be 0 ~ 20% MDQ silicone resin.When D unit ratio was 10%, tensile strength was all relative maximum with elongation at break, and still, the weak point of this invention is that gained MDQ resin specific refractory power is low, is not more than 1.46;
Contain in the molecule in preparation method's document of MDQ silicone resin of phenyl functional group and have been reported.Chinese invention patent CN 101805562 A disclose hydroxyl (HO-) or the alkoxyl group (preparation method of MDQ resin OR), its with hexamethyldisiloxane, methyl silicate and dichloromethyl phenylsilane as raw material, take toluene as solvent, prepare by hydrolytic condensation that solid content is about 50%, structural formula is [Me
3SiO
1/2]
0.35[MePhSiO
2/2]
0.2[SiO
4/2]
0.35[HO]
0.06The MDQ resin of hydroxyl; Adopt methyltrimethoxy silane and acetic acid that the MDQ resin of hydroxyl is further processed under heating up, obtain containing alkoxyl group MDQ resin; Then with the hydroxyl of preparation or the MDQ silicone resin component that contains alkoxyl group with contain linear hydroxyl-terminated silicone oil component, White Carbon black component, linking agent component, catalyst component and tackifier component mixed preparing obtain different viscosity, varying strength and toughness, strong adhesive force the insulated type moisture-curable be coated with dressing; this is coated with dressing and has the better protecting performance, the device of various electronic devices and components, line plate circuit plate and charged work is all had the protection effects such as good waterproof, protection against the tide, shockproof, insulation, anti-aging, dustproof, protection against corrosion.But gained MDQ is 50% solution; Its purposes is the coating material by moisture-curable; MDQ hydroxyl or alkoxyl group should be invented simultaneously, silicon hydrogen addition curing can not be passed through;
Japanese Patent JP 07228701A discloses the MDQ silicone resin preparation method that a kind of D chain link contains the Si-H group, and it will have structure and be (Me
3SiO
1/2)
a(SiO
4/2)
bResin dissolves in organic solvent, under an acidic catalyst effect, carry out dehydrating condensation, then with have (MeHSiO
2/2)
c(Me
2SiO
2/2)
d(c=1 ~ 100; D=0 ~ 100) polydiorganosiloxane of structure re-starts balanced reaction, obtains structure and is (Me
3SiO
1/2)
a(MeHSiO
2/2)
y(Me
2SiO
2/2)
z(SiO
4/2) the hydrogeneous MDQ silicone resin of D chain link.But this invention does not contain phenyl, though can carry out silicon hydrogen addition curing by silicon hydrogen, specific refractory power is low.
Compare with the containing hydrogen silicone oil linking agent of high refractive index organosilicon body material and high refractive index, but the phenyl MDQ type silicon resin that solidifies as the chemically crosslinked of rubber-type packaged material reinforced filling still is in the research and development, have been reported although contain preparation method's document of the MDQ silicone resin of phenyl and the siliceous hydrogen functional group's of D chain link methyl MDQ silicone resin, can have no report by the phenyl MDQ type silicon resin of the addition-crosslinked curing of silicon hydrogen.
Summary of the invention
Low and can not solidify by chemically crosslinked and improve simultaneously rubber-type packaged material optical property that silicone resin strengthens and the problem of mechanical property for solving MDQ silicone resin specific refractory power, but the present invention proposes the phenyl MDQ type silicon resin that a kind of chemically crosslinked is solidified, the present invention not only improves the mechanical property of the rubber-type packaged material of MDQ silicone resin reinforcement, also improves the optical property of rubber-type packaged material.Another object of the present invention is that reaction conditions is gentle, and technique is simple, is very suitable for large-scale commercial production.
The present invention is achieved by the following technical solutions: but the phenyl MDQ type silicon resin that a kind of chemically crosslinked is solidified, but the phenyl MDQ type silicon resin that described chemically crosslinked is solidified is with hexamethyldisiloxane and 1, the 3-divinyl tetramethyl disiloxane is as end-capping reagent, the aminomethyl phenyl diethoxy silane is originated as the D chain link, tetraethoxy is originated as the Q chain link, aqueous ethanolic solution is as reaction solvent, under the hydrochloric acid catalysis effect, be prepared from by the cohydrolysis condensation process, but the structural formula of the phenyl MDQ type silicon resin that chemically crosslinked is solidified is: [Me
3SiO
1/2]
a[Me
2ViSiO
1/2]
b[MePhSiO
2/2]
c[SiO
4/2]
d, a=0.08 ~ 0.25, b=0.11 ~ 0.20, c=0.07 ~ 0.26, d=0.50 ~ 0.53, and a+b+c+d=1.
The specific refractory power of resin depends on the content of high molar refraction functional group in the molecular resin.The Lorentz-Lorenz molar refraction degree of methyl and vinyl is less, its numerical value is respectively 5.718 and 5.033, the Lorentz-Lorenz molar refraction degree of phenyl reaches 25.463(J. A. Dean, Lan Shi chemistry handbook, Beijing: Science Press, 1991.), therefore phenyl is introduced the specific refractory power that can significantly improve resin extender in the molecular resin.With the reinforced filling of resin as the close organosilicon base polymer of specific refractory power, as linking agent, sulfidization molding after can obtain optically transparent packaged material under the effect of silicon hydrogen addition catalyst with the close containing hydrogen silicone oil of specific refractory power.Except in molecular resin, introducing the phenyl functional group of high molar refraction, introduce simultaneously silico ethylene base or the silicon hydrogen base that can participate in addition reaction of silicon with hydrogen, then not only can improve the packaged material optical property, and participate in the silicon hydrogen addition curing reaction of silicon rubber by molecular resin, improve the mechanical property of packaged material.
The silicone resin of MDQ type is a kind of in the MQ silicone resin, and it is by single functionality silica chain link (R
1R
2R
3SiO
1/2, the M chain link), two functionality silica chain link (R
4R
5SiO
2/2, the D chain link) and four functionality silica chain link (SiO
4/2, the Q chain link) silicoorganic compound form through cohydrolysis-polycondensation.When the organo-functional group that connects on the Siliciumatom is vinyl or hydrogen, under the catalyst for addition reaction of hydrogen and silicon effect, vinyl MDQ silicone resin can carry out chemically crosslinked by the linking agent that contains reactive hydrogen in the silico ethylene base in the molecule and the silicon rubber system, the MDQ silicone resin that contains reactive hydrogen also can carry out chemically crosslinked by the silicon hydrogen base in the molecule and the vinyl silicone oil in the silicon rubber system, thereby during as the reinforced filling of addition-type silicon rubber, can improve by chemical crosslink reaction the mechanical property of silicon rubber with the MDQ type silicon resin of siliceous vinyl or silicon hydrogen base.
The present invention is with 1, the 3-divinyl tetramethyl disiloxane is as end-capping reagent, the aminomethyl phenyl diethoxy silane is as the D chain link source that contains phenyl, prepare the MDQ type silicon resin that the siliceous vinyl of M chain link and D chain link contain phenyl by the cohydrolysis method of condensing, utilize the silico ethylene base to participate in the silicon hydrogen addition vulcanization process of silicon rubber, improve the mechanical property of the rubber-type packaged material of MDQ silicone resin enhancing, utilize the phenyl functional group of high molar refraction, improve the specific refractory power of MDQ silicone resin, dwindled the difference between filler and silicon rubber matrix material and the linking agent specific refractory power, with the filler of MDQ resin as the silicon rubber matrix, not only improve the mechanical property of the rubber-type packaged material of MDQ silicone resin reinforcement, also improve the optical property of rubber-type packaged material, can prepare satisfactory mechanical property, optical clear, the rubber-type packaged material of high refractive index, with its packaged material as great power LED, can improve the light efficiency of semiconductor lighting device.
But the preparation method of the phenyl MDQ type silicon resin that a kind of chemically crosslinked is solidified carries out as follows:
1) in the there-necked flask with mechanical stirrer, thermometer and constant pressure funnel, stirs after adding entry and dehydrated alcohol;
2) add hexamethyldisiloxane, 1 under agitation condition, then the mixing solutions that 3-divinyl tetramethyl disiloxane and aminomethyl phenyl diethoxy silane form drips hydrochloric acid; As preferably, hydrochloric acid is concentrated hydrochloric acid; The consumption of concentrated hydrochloric acid is few like this, and the waste liquid that the back extraction is discharged will lack; The mass concentration of concentrated hydrochloric acid is 36 ~ 38%.
3) during rising temperature to 40 ~ 60 ℃, drip tetraethoxy, then keep reaction 0.5 ~ 5h at 60 ~ 90 ℃; Be cooled to 50 ~ 70 ℃, add the toluene extraction, then be cooled to room temperature, be washed to neutrality; Add Calcium Chloride Powder Anhydrous and be dried to clear, filter desalination, but rotary evaporation obtains the phenyl MDQ type silicon resin that a kind of chemically crosslinked is solidified after removing toluene solvant.
The mass ratio of water and dehydrated alcohol is 1.0 ~ 5.0:1 in the described step 1), and as preferably, the mass ratio of water and dehydrated alcohol is 2.0 ~ 2.5:1;
Step 2) hexamethyldisiloxane and 1 in, the mol ratio of 3-divinyl tetramethyl disiloxane is 0.2 ~ 2.0:1, hexamethyldisiloxane, 1, the molar weight sum of 3-divinyl tetramethyl disiloxane and the mol ratio of aminomethyl phenyl diethoxy silane are 0.2 ~ 4.0:1, the mol ratio of hydrochloric acid and aminomethyl phenyl diethoxy silane is 0.5 ~ 5.0:1, as preferably, hexamethyldisiloxane and 1, the mol ratio of 3-divinyl tetramethyl disiloxane is 0.4 ~ 1.5:1, hexamethyldisiloxane, 1, the molar weight sum of 3-divinyl tetramethyl disiloxane and the mol ratio of aminomethyl phenyl diethoxy silane are 0.3 ~ 3.0:1, and the mol ratio of hydrochloric acid and aminomethyl phenyl diethoxy silane is 0.9 ~ 3.5:1;
Dehydrated alcohol and step 2 in the step 1)) in the mol ratio of hydrochloric acid be 1.0 ~ 5.0:1, as preferably, mol ratio is 2.0 ~ 4.0:1;
Tetraethoxy and step 2 in the step 3)) in the mol ratio of aminomethyl phenyl diethoxy silane be 1.0 ~ 10.0:1, as preferably, mol ratio is 1.8 ~ 7.2:1.
The mol ratio of water is 0.1 ~ 1.0:1 in extraction agent toluene and the step 1), and as preferably, molar ratio is 0.2 ~ 0.8:1.
Reaction equation of the present invention is as follows, and its Chinese style (1) expression hexamethyldisiloxane hydrolysis reaction under the hydrochloric acid catalysis effect generates trimethyl silanol; Formula (2) expression 1,3-divinyl tetramethyl disiloxane hydrolysis reaction under the hydrochloric acid catalysis effect generates dimethyl vinyl silanol, formula (3) expression aminomethyl phenyl diethoxy silane generates the silanol performed polymer that the D chain link contains aminomethyl phenyl silica chain link under the hydrochloric acid catalysis effect, formula (4) expression tetraethoxy hydrolysis reaction under the hydrochloric acid catalysis effect generates the silanol performed polymer of Q chain link, and formula (5) the various silanols of expression or silanol performed polymer generate the MDQ silicone resin by the condensation polymerization reaction under the hydrochloric acid effect.
（4）
The present invention possesses the phenyl functional group of silico ethylene base and high refractive index simultaneously, can pass through silicon hydrogen addition curing, as filler, can improve the physical strength of silicon rubber composite material with it, also can improve the optical property (specific refractory power) of silicon rubber.Compared with prior art, the invention has the beneficial effects as follows:
(1) not only improves the mechanical property of the rubber-type packaged material of MDQ silicone resin reinforcement, and improve the optical property of rubber-type packaged material.
(2) present method reaction conditions is gentle, and technique is simple, is very suitable for large-scale commercial production.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment not limiting the scope of the invention that used raw material is commercial product among the embodiment.
Embodiment 1
Mechanical stirrer is being housed, in the there-necked flask of 250 ml of thermometer and constant pressure funnel, add 12.4g(0.333 mol) deionized water and 5.4g(0.117 mol) stir behind the dehydrated alcohol, under agitation add again 0.65 g hexamethyldisiloxane (0.004 mol), (3.6g 0.0194 mol) 1,3-divinyl tetramethyl disiloxane and 24.0g(0.1143 mol) mixing solutions that forms of aminomethyl phenyl diethoxy silane, then drip 1.2mL concentration and be 36% concentrated hydrochloric acid (0.0388 mol), during rising temperature to 40 ℃, in 10min, dripping 24.0g(0.1154 mol) then tetraethoxy keep reaction 3h at 80 ℃.Add the extraction of 25ml toluene when being cooled to 50 ℃, then be cooled to room temperature, be washed to neutrality, add Calcium Chloride Powder Anhydrous and be dried to clear, filter desalination, but rotary evaporation obtains the phenyl MDQ type silicon resin that chemically crosslinked is solidified after removing toluene solvant, the structural formula of MDQ resin is [Me
3SiO
1/2]
0.13[Me
2ViSiO
1/2]
0.20[MePhSiO
2/2]
0.16[SiO
4/2]
0.51, its refractive index n
D 25Be 1.4665, number average molecular mass 1403g/mol, polydispersity index 1.46.
Embodiment 2
In the there-necked flask of 250 ml that mechanical stirrer, thermometer and constant pressure funnel are housed, add 12.2g(0.678 mol) deionized water and 5.3g(0.1152 mol) stir behind the dehydrated alcohol, under agitation add again 3.1g(0.0191 mol) hexamethyldisiloxane, 3.2g(0.0172 mol) 1,3-divinyl tetramethyl disiloxane and 4.7g(0.0224 mol) mixing solutions that the aminomethyl phenyl diethoxy silane forms, then drip
3.4ML concentration is 36% concentrated hydrochloric acid (0.1098 mol), during rising temperature to 60 ℃, drips 21.0g(0.1010 mol in 20min) then tetraethoxy keep reaction 1h at 90 ℃.Add the extraction of 25ml toluene when being cooled to 70 ℃, then be cooled to room temperature, be washed to neutrality, add Calcium Chloride Powder Anhydrous and be dried to clear, filter desalination, but rotary evaporation obtains the phenyl MDQ type silicon resin that chemically crosslinked is solidified after removing toluene solvant, the structural formula of MDQ resin is [Me
3SiO
1/2]
0.20[Me
2ViSiO
1/2]
0.18[MePhSiO
2/2]
0.11[SiO
4/2]
0.51, its refractive index n
D 25Be 1.4563, number average molecular mass 1688g/mol, polydispersity index 1.86.
Embodiment 3
Mechanical stirrer is being housed, in the there-necked flask of 250 ml of thermometer and constant pressure funnel, add 12.1g(0.672 mol) deionized water and 5.3g(0.1152 mol) stir behind the dehydrated alcohol, under agitation add again 1.2g(0.0074 mol) hexamethyldisiloxane, (3.3g 0.0177 mol) 1,3-divinyl tetramethyl disiloxane and 8.5g(0.0405 mol) mixing solutions that forms of aminomethyl phenyl diethoxy silane, then drip 1.5mL concentration and be 36% concentrated hydrochloric acid (0.0484 mol), during rising temperature to 50 ℃, in 30min, dripping 20.9g(0.1005 mol) then tetraethoxy keep reaction 4h at 60 ℃.Add the extraction of 25ml toluene when being cooled to 50 ℃, then be cooled to room temperature, be washed to neutrality, add Calcium Chloride Powder Anhydrous and be dried to clear, filter desalination, but rotary evaporation obtains the phenyl MDQ type silicon resin that chemically crosslinked is solidified after removing toluene solvant, the structural formula of MDQ resin is [Me
3SiO
1/2]
0.08[Me
2ViSiO
1/2]
0.19[MePhSiO
2/2]
0.21[SiO
4/2]
0.53, its refractive index n
D 25Be 1.4789, number average molecular mass 1287g/mol, polydispersity index 1.31.
Embodiment 4
Mechanical stirrer is being housed, in the there-necked flask of 250 ml of thermometer and constant pressure funnel, add 12.2g(0.678 mol) deionized water and 5.1g(0.1109 mol) stir behind the dehydrated alcohol, under agitation add again 5.9g(0.0364 mol) hexamethyldisiloxane, (3.4g 0.0183 mol) 1,3-divinyl tetramethyl disiloxane and 2.9g(0.0138 mol) mixing solutions that forms of aminomethyl phenyl diethoxy silane, then drip 1.4mL concentration and be 36% concentrated hydrochloric acid (0.0452 mol), during rising temperature to 45 ℃, in 10min, dripping 28.7g(0.1380 mol) then tetraethoxy keep reaction 5h at 75 ℃.Add the extraction of 25ml toluene when being cooled to 60 ℃, then be cooled to room temperature, be washed to neutrality, add Calcium Chloride Powder Anhydrous and be dried to clear, filter desalination, but rotary evaporation obtains the phenyl MDQ type silicon resin that chemically crosslinked is solidified after removing toluene solvant, the structural formula of MDQ resin is [Me
3SiO
1/2]
0.25[Me
2ViSiO
1/2]
0.18[MePhSiO
2/2]
0.07[SiO
4/2]
0.50, its refractive index n
D 25Be 1.4849, number average molecular mass 1404g/mol, polydispersity index 1.30.
Embodiment 5
Mechanical stirrer is being housed, in the there-necked flask of 250 ml of thermometer and constant pressure funnel, add 12.3g(0.683 mol) deionized water and 5.9g(0.1283 mol) stir behind the dehydrated alcohol, under agitation add again 1.6g(0.0099 mol) hexamethyldisiloxane, 1.9g(0.0102 mol) 1,3-divinyl tetramethyl disiloxane and 10.6g(0.0505 mol) mixing solutions that forms of aminomethyl phenyl diethoxy silane, then drip 0.8mL concentration and be 36% concentrated hydrochloric acid (0.026 mol), during rising temperature to 40 ℃, in 10min, dripping 20.8g(0.1 mol) then tetraethoxy keep reaction 5h at 60 ℃.Add the extraction of 25ml toluene when being cooled to 50 ℃, then be cooled to room temperature, be washed to neutrality, add Calcium Chloride Powder Anhydrous and be dried to clear, filter desalination, but rotary evaporation obtains the phenyl MDQ type silicon resin that chemically crosslinked is solidified after removing toluene solvant, the structural formula of MDQ resin is [Me
3SiO
1/2]
0.11[Me
2ViSiO
1/2]
0.11[MePhSiO
2/2]
0.26[SiO
4/2]
0.52, its refractive index n
D 25Be 1.4876, number average molecular mass 3002g/mol, polydispersity index 1.15.
Claims (7)
1. but the phenyl MDQ type silicon resin that solidifies of a chemically crosslinked, it is characterized in that: but the phenyl MDQ type silicon resin that described chemically crosslinked is solidified is with hexamethyldisiloxane and 1, the 3-divinyl tetramethyl disiloxane is as end-capping reagent, the aminomethyl phenyl diethoxy silane is originated as the D chain link, tetraethoxy is originated as the Q chain link, aqueous ethanolic solution is prepared from by the cohydrolysis condensation process under the hydrochloric acid catalysis effect as reaction solvent
But the structural formula of the phenyl MDQ type silicon resin that chemically crosslinked is solidified is: [Me
3SiO
1/2]
a[Me
2ViSiO
1/2]
b[MePhSiO
2/2]
c[SiO
4/2]
d, wherein, a=0.08 ~ 0.25, b=0.11 ~ 0.20, c=0.07 ~ 0.26, d=0.50 ~ 0.53, and a+b+c+d=1.
2. but the preparation method of the phenyl MDQ type silicon resin that solidifies of a chemically crosslinked is characterized in that described preparation method carries out as follows:
In the there-necked flask with mechanical stirrer, thermometer and constant pressure funnel, stir after adding entry and dehydrated alcohol;
Add hexamethyldisiloxane, 1 under agitation condition, then the mixing solutions that 3-divinyl tetramethyl disiloxane and aminomethyl phenyl diethoxy silane form drips hydrochloric acid;
Rising temperature to 40 ~ 60 ℃ drip tetraethoxy, then keep reaction 0.5 ~ 5h at 60 ~ 90 ℃, add the toluene extraction when being cooled to 50 ~ 70 ℃, then are cooled to room temperature, are washed to neutrality; Add Calcium Chloride Powder Anhydrous and be dried to clear, filter desalination, but rotary evaporation has obtained the phenyl MDQ type silicon resin that a kind of chemically crosslinked is solidified after removing toluene.
3. but the preparation method of the phenyl MDQ type silicon resin of a kind of chemically crosslinked curing according to claim 2 is characterized in that the mass ratio of water and dehydrated alcohol is 1.0 ~ 5.0:1 in the described step 1).
4. but the preparation method of the phenyl MDQ type silicon resin that solidifies of a kind of chemically crosslinked according to claim 2, it is characterized in that, step 2) hexamethyldisiloxane and 1 in, the mol ratio of 3-divinyl tetramethyl disiloxane is 0.2 ~ 2.0:1, hexamethyldisiloxane and 1, the molar weight sum of 3-divinyl tetramethyl disiloxane and the mol ratio of aminomethyl phenyl diethoxy silane are 0.2 ~ 4.0:1, and the mol ratio of hydrochloric acid and aminomethyl phenyl diethoxy silane is 0.5 ~ 5.0:1.
5. but according to claim 2 or the preparation method of the phenyl MDQ type silicon resin that solidifies of 3 or 4 described a kind of chemically crosslinkeds, it is characterized in that dehydrated alcohol and step 2 in the step 1)) mol ratio of middle hydrochloric acid is 1.0 ~ 5.0:1.
6. but according to claim 2 or the preparation method of the phenyl MDQ type silicon resin that solidifies of 4 described a kind of chemically crosslinkeds, it is characterized in that tetraethoxy and step 2 in the step 3)) mol ratio of middle aminomethyl phenyl diethoxy silane is 1.0 ~ 10.0:1.
7. but the preparation method of the phenyl MDQ type silicon resin that solidifies of a kind of chemically crosslinked according to claim 2 is characterized in that, in the step 3) in extraction agent toluene and the step 1) mol ratio of water be 0.1 ~ 1.0:1.
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| CN104448318A (en) * | 2014-11-27 | 2015-03-25 | 深圳市森日有机硅材料有限公司 | MDQ phenyl vinyl silicone resin and preparation method thereof |
| CN104892938A (en) * | 2015-06-26 | 2015-09-09 | 深圳市森日有机硅材料有限公司 | MDQ phenyl hydrogen-containing silicon resin and preparing method thereof |
| CN106084792A (en) * | 2016-04-16 | 2016-11-09 | 杭州师范大学 | A kind of flexible dielectric silicone resin composite material and preparation method thereof |
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| CN108129509A (en) * | 2017-12-25 | 2018-06-08 | 湖北泓肽生物科技有限公司 | It is a kind of to recycle the method for waste generated in protected silane reaction process |
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| CN110698674A (en) * | 2019-02-18 | 2020-01-17 | 杭州师范大学 | Fluorine-containing MDQ type silicon resin capable of being chemically crosslinked and cured and preparation method thereof |
| CN112745505A (en) * | 2020-12-28 | 2021-05-04 | 广东标美硅氟新材料有限公司 | Alkyl modified MDQ type silicon resin and preparation method and application thereof |
| CN113248711A (en) * | 2021-03-26 | 2021-08-13 | 山东大易化工有限公司 | Method for recycling acidic waste liquid in production process of silicon resin |
| CN115197427A (en) * | 2021-04-13 | 2022-10-18 | 中蓝晨光化工有限公司 | High-strength solvent-free room-temperature curing organic silicon resin and preparation method thereof |
| CN115746304A (en) * | 2022-12-07 | 2023-03-07 | 嘉兴联合化学有限公司 | Method for preparing phenyl silicone resin without solvent and application thereof |
| CN117467142A (en) * | 2023-11-23 | 2024-01-30 | 广东鼎立森新材料有限公司 | Preparation method of methyl phenyl silicone resin block copolymer |
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| WO2016082287A1 (en) * | 2014-11-27 | 2016-06-02 | 深圳市森日有机硅材料有限公司 | Mdq phenyl vinyl silicone resin and preparation method therefor |
| CN104448318A (en) * | 2014-11-27 | 2015-03-25 | 深圳市森日有机硅材料有限公司 | MDQ phenyl vinyl silicone resin and preparation method thereof |
| CN104892938A (en) * | 2015-06-26 | 2015-09-09 | 深圳市森日有机硅材料有限公司 | MDQ phenyl hydrogen-containing silicon resin and preparing method thereof |
| CN106084792A (en) * | 2016-04-16 | 2016-11-09 | 杭州师范大学 | A kind of flexible dielectric silicone resin composite material and preparation method thereof |
| CN106497507A (en) * | 2016-10-12 | 2017-03-15 | 烟台德邦先进硅材料有限公司 | A kind of UV that is used for encapsulates organic silicon packaging glue compositionss and preparation method thereof |
| CN106700077A (en) * | 2016-11-11 | 2017-05-24 | 烟台德邦先进硅材料有限公司 | Preparation method of high-temperature-resistant anti-cracking MDQ silicon resin |
| CN108129509A (en) * | 2017-12-25 | 2018-06-08 | 湖北泓肽生物科技有限公司 | It is a kind of to recycle the method for waste generated in protected silane reaction process |
| CN109722218B (en) * | 2018-12-25 | 2021-05-04 | 烟台德邦科技股份有限公司 | Electrolyte-resistant sealant and preparation method thereof |
| CN109722218A (en) * | 2018-12-25 | 2019-05-07 | 烟台德邦科技有限公司 | A kind of electrolyte resistance sealant and preparation method thereof |
| CN110698674A (en) * | 2019-02-18 | 2020-01-17 | 杭州师范大学 | Fluorine-containing MDQ type silicon resin capable of being chemically crosslinked and cured and preparation method thereof |
| CN112745505A (en) * | 2020-12-28 | 2021-05-04 | 广东标美硅氟新材料有限公司 | Alkyl modified MDQ type silicon resin and preparation method and application thereof |
| CN112745505B (en) * | 2020-12-28 | 2022-05-03 | 广东标美硅氟新材料有限公司 | Alkyl modified MDQ type silicon resin and preparation method and application thereof |
| CN113248711A (en) * | 2021-03-26 | 2021-08-13 | 山东大易化工有限公司 | Method for recycling acidic waste liquid in production process of silicon resin |
| CN113248711B (en) * | 2021-03-26 | 2022-06-03 | 山东大易化工有限公司 | Method for recycling acidic waste liquid in production process of silicon resin |
| CN115197427A (en) * | 2021-04-13 | 2022-10-18 | 中蓝晨光化工有限公司 | High-strength solvent-free room-temperature curing organic silicon resin and preparation method thereof |
| CN115197427B (en) * | 2021-04-13 | 2023-08-08 | 中蓝晨光化工有限公司 | High-strength solvent-free room-temperature curing organic silicon resin and preparation method thereof |
| CN115746304A (en) * | 2022-12-07 | 2023-03-07 | 嘉兴联合化学有限公司 | Method for preparing phenyl silicone resin without solvent and application thereof |
| CN115746304B (en) * | 2022-12-07 | 2023-08-04 | 嘉兴联合化学有限公司 | Method for preparing phenyl silicone resin without solvent and application thereof |
| CN117467142A (en) * | 2023-11-23 | 2024-01-30 | 广东鼎立森新材料有限公司 | Preparation method of methyl phenyl silicone resin block copolymer |
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