CN101935328B - Preparation method of methyl phenyl mixed cyclosiloxane - Google Patents
Preparation method of methyl phenyl mixed cyclosiloxane Download PDFInfo
- Publication number
- CN101935328B CN101935328B CN2010102390140A CN201010239014A CN101935328B CN 101935328 B CN101935328 B CN 101935328B CN 2010102390140 A CN2010102390140 A CN 2010102390140A CN 201010239014 A CN201010239014 A CN 201010239014A CN 101935328 B CN101935328 B CN 101935328B
- Authority
- CN
- China
- Prior art keywords
- aminomethyl phenyl
- catalyst
- cracking
- phenyl
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a preparation method of methyl phenyl mixed cyclosiloxane, mainly aiming at solving the technical problems that a preparation process does not need to carry out washing neutralization or add a neutralizer and a product does not contain trifunctional impurities. The preparation method of the methyl phenyl mixed cyclosiloxane comprises the following steps of: (1) carrying out hydrolysis reaction on methyl phenyl dialkoxy silicane with a catalyst and deionized water, receiving an alcohol-water mixture generated in the hydrolysis reaction, reducing temperature, and standing for demixing; (2) removing a solid super acidic catalyst to obtain filter liquor by filtering a lower layer; (3) adding methylbenzene with volume 0.2-5 times larger than that of the filter liquor to the obtained filter liquor, dewatering, and steaming to eliminate the methylbenzene to obtain hydrolysate oil; and (4) adding a cracking catalyst to the hydrolysate oil to carry out cracking at 200-320 DEG C and under 0.096 MPa, and collecting a cracking product so as to obtain the methyl phenyl mixed cyclosiloxane, wherein the using amount of the cracking catalyst is 0.01-50 percent by weight of the mass of the hydrolysate oil.
Description
Technical field
The present invention relates to organic chemistry filed, specifically is a kind of preparation method of methyl-phenyl hybrid ring siloxane.
Background technology
Methyl phenyl ring siloxane is meant the ring-like siloxanes that contains methyl and phenyl on the Siliciumatom simultaneously, but the general structure simple table is shown (MePhSiO) n (n >=3).High purity, the methyl phenyl ring siloxane that does not contain trifunctional impurity are one of raw materials of preparation aminomethyl phenyl high-temperature silicon disulfide rubber.In addition; Methyl phenyl ring siloxane has good physiology inertia; Good surfactivity, stability to aging, ultra-violet radiation resisting property, printing opacity, performance such as nonpoisonous and tasteless can be widely used in the host and the auxiliary agent of makeup, can also be used for medicine and medical and health industry.
Use the dichloromethyl phenylsilane hydrolysis, high temperature is reset or cracking then, can obtain methyl phenyl ring siloxane.Lewis [J. Am. Chem. Soc., 1948,70; 1115-1117], [J. Am. Chem. Soc., 1948,70 such as Young; 3758-3764] with the dichloromethyl phenylsilane hydrolysis, at high temperature add thermal rearrangement then, the cut under receiving 2mmHg/295 ℃; Prepared methyl-phenyl hybrid ring siloxane, but productive rate has only 30-35%.People add thermal cracking catalyst again, have improved the yield of cyclosiloxane.[Synthesis and Characterization of Cis-and Trans-Trimethyltriphenyl cyclotrisiloxane such as Ahn; Journal of Inorganic and Organometallic Polymers] be raw material with dichloromethyl phenylsilane and zinc oxide, hydrolysis, Pintsch process have prepared the aminomethyl phenyl cyclotrisiloxane.In 70～80 ℃ of following hydrolysis, the hydrolysing oil washing is to neutral with dichloromethyl phenylsilane for Guinet etc. [1969, US 3484469]; After the drying; The alkaline carbonate of adding 0.05%～6% is being lower than under the 10mmHg 250～290 ℃ of following thermo-crackings as catalyzer; Obtain methyl phenyl ring siloxane, 40～70% is the Fourth Ring body in the product.Kuznetsova etc. [1971; U S 3558681] with dichloromethyl phenylsilane hydrolysis under vigorous stirring; Hydrolysing oil is washed to neutrality; It is dry to add Calcium Chloride Powder Anhydrous, adds 0.01～1% Lithium Hydroxide MonoHydrate or about 1～10% silanol lithium then and under 1～2mmHg, is heated to 250 ℃, and product yield is up to about 90%.Come state's bridge etc. [2009, CN101503421] with dichloromethyl phenylsilane with after aromatic hydrocarbons mixes, be added drop-wise in the heterogeneous mixed solvent system that mixes mutually, the reaction that under 0～30 ℃, is hydrolyzed, steam desolventize after, the adding catalyzer can obtain methyl phenyl ring siloxane.
The dichloromethyl phenylsilane hydrolysis can produce a large amount of HCl gas, need produce a lot of spent acid waste water through washing, N-process, contaminate environment, and labour intensity is big.In addition; Owing to contain phenyl-trichloro-silicane to some extent in the dichloromethyl phenylsilane; Phenyl-trichloro-silicane ground content can because both boiling points are close, be respectively 205.0 ℃ (101.3KPa) and 201.0 ℃ (101.3KPa) from 0.1%～10%; Even the employing rectifying separation also is difficult to the dichloromethyl phenylsilane that high-level efficiency obtains not contain phenyl-trichloro-silicane.Thereby inevitably there is trifunctional impurity in the methyl-phenyl hybrid ring siloxane for preparing with dichloromethyl phenylsilane.The existence of trifunctional impurity, product will reduce the performance of aminomethyl phenyl hot-vulcanized silicone rubber when the aminomethyl phenyl high-temperature silicon disulfide rubber raw material, in addition occur crosslinked with climb the roller phenomenon; Product is as LED encapsulation during with the organosilicon material raw material, is difficult to obtain refractive index and is higher than 1.50 LED and encapsulates and use organosilicon material.
Li Meijiang etc. [2008, CN101125860] are to contain phenyl silica trifunctional chain link (SiPhO
1.5) be T
PMethyl phenyl silicone be raw material method through thermo-cracking under base catalysis, also prepared methyl phenyl ring siloxane.Adopt pyrolysis method, need to prepare qualified cyclosiloxane through operation such as catalytic pyrolysis, rectifying, need operation at high temperature, equipment to be easy to damage, operating environment is poor, complex process, and cost is high.
With aminomethyl phenyl dialkoxy silicane hydrolysis method, also can prepare methyl phenyl ring siloxane.Razzano [1998, U S 5739370] has reported dichloromethyl phenylsilane and alcohol reaction, obtains organoalkoxysilane, uses the very alkali metal hydroxide such as the LiOH of lower concentration then, NaOH, and catalytic pyrolysiss such as KOH obtain methyl phenyl ring siloxane.Compton etc. [2000; U S 6160151] reported that then (X=Cl, Br I) react with organoalkoxysilane and Grignard reagent PhMgX in THF and YLENE mixed solvent; Filtration residue; With the clear liquid vacuum fractionation, obtain the aminomethyl phenyl diethoxy silane, hydrolysis obtains symmetric tetramethyl tetraphenyl cyclotetrasiloxane under alkaline condition then.
Owing to contain phenyl-trichloro-silicane to some extent in the raw material dichloromethyl phenylsilane of preparation aminomethyl phenyl organoalkoxysilane, also be difficult to the dichloromethyl phenylsilane that high-level efficiency obtains not contain phenyl-trichloro-silicane.The mixing liquid that Wu Chuan etc. [2009, CN101503422] form with the aqueous solution of highly purified aminomethyl phenyl diethoxy silane and catalyzer by a certain percentage joins band and is equipped with in the reactor drum of separator column and cat head still head of filler, and reaction is hydrolyzed under normal pressure and 70～125 ℃; After hydrolysing oil is neutralized to neutrality; Water layer is separated with oil reservoir, and with toluene as entrainment agent, after small amount of moisture remaining in the oil reservoir removed; Normal pressure or decompression heat up down and remove toluene; Obtain the aminomethyl phenyl mixed methylcyclosiloxane, do not contain trifunctional impurity in the product, the Siliciumatom utilization ratio is high in hydrolytic condensation and the cracking process.
After the hydrolysis of above-mentioned aminomethyl phenyl dialkoxy silicane again thermo-cracking prepare the method for methyl phenyl ring siloxane, in hydrolytic process, need washing or add the neutralizing agent neutralization to make hydrolysing oil be neutral.If with the washing neutralization, also can produce more a large amount of waste water, labour intensity is bigger.If use neutralizing agent; Then can in hydrolysing oil, introduce more a large amount of metals ions; These metals ions can be carried secretly by steam in thermal cracking processes; And in the entering product, can make that like this metal ion content is higher in the methyl-phenyl hybrid ring siloxane, influence the application of product in the electronic apparatus packaged material that it makes as raw material.
Summary of the invention
The technical issues that need to address of the present invention are, provide a kind of and need not wash neutralization or add neutralizing agent, only need to filter and can catalyzer be separated from hydrolysis reaction system, and do not contain the new preparation method of the methyl-phenyl hybrid ring siloxane of trifunctional impurity.
Adopt rare-earth solid superacid SO
4 2-/ M
xO
y/ Ln
3+Making catalyzer is key problem in technology of the present invention.Solid super-strong acid is meant the acid that the solid surface strength of acid is stronger than 100% sulfuric acid, i.e. Hammett acidity function Ho < 11.9 acid.Solid super-strong acid has that preparation is simple, convenient for storing, catalytic activity are high, free from environmental pollution, not etching apparatus, advantage such as can regenerate and recycle; Reaction finishes the back only to be needed to filter to realize that just catalyzer separates with reaction product; Be a kind of commercial catalysts that has a extensive future, be applied in the various organic reactions.At SO
4 2-/ M
xO
yA certain amount of rare earth ion of doping in the type solid super-strong acid, preparation rare-earth solid superacid SO
4 2-/ M
xO
y/ Ln
3+(Ln
3+Represent rare earth ion), can be regarded as modification, promptly at SO to solid super-strong acid
4 2-/ M
xO
yThe surface both adsorbed SO
4 2-, adsorbed a certain amount of rare earth ion Ln again
3+, one side Ln
3+Itself be exactly Lewis acid, compare SO
4 2-/ M
xO
yMany a part of lewis acid centers.On the other hand; Load micro-rare earth, be equivalent in the metals ion placed around electrophilic source, the positive charge on the metals ion is increased; Rare earth and original atoms metal produce synergistic effect, help further improving catalyst activity.
The preparation method of methyl-phenyl hybrid ring siloxane of the present invention is characterized in that as follows:
1) aminomethyl phenyl dialkoxy silicane and catalyzer and deionized water are joined in the reactor drum of temperature control platinum probe, the reaction that under normal pressure and 60～130 ℃, is hydrolyzed receives alcohol-water mixture that reaction generates, the refractive index n of mensuration distillate
D 25, work as n
D 25Near 1.3325 o'clock, stop heating, cooling, standing demix; Wherein catalyst levels is that (be preferably 3～9wt%), the mass ratio of aminomethyl phenyl dialkoxy silicane and deionized water is 1:0.2～5 for 1～15wt% of aminomethyl phenyl dialkoxy silicane;
Described aminomethyl phenyl dialkoxy silicane is one or more the mixture in aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dipropoxy silane, aminomethyl phenyl diisopropoxy silane, the aminomethyl phenyl dibutoxy silane.
2) reaction mixture with standing demix separates, and solid super acid catalyst is removed through suction filtration by lower floor, obtains filtrating;
3) in gained filtrating, add the toluene of 0.2～5 times of filtrate volume, dewater, after the water Ex-all, steam and remove toluene, acquisition exsiccant hydrolysing oil with the water trap normal pressure;
4) one or more (being preferably LiOH or its hydrate) among adding catalyst for cracking LiOH or its hydrate, NaOH, KOH, RbOH, the CsOH in the dry hydrolysing oil of gained; Under 200～320 ℃, 0.096MPa, carry out cracking; Collect split product, promptly get methyl-phenyl hybrid ring siloxane; Wherein the catalyst for cracking consumption is that 0.01～50wt% of hydrolysing oil quality (is preferably 0.05～10wt%);
Described catalyzer is for having general formula SO
4 2-/ M
xO
y/ Ln
3+Rare-earth solid superacid, M in the formula
xO
yBe TiO
2, Al
2O
3, SiO
2, ZrO
2In one or more mixture (be preferably TiO
2), thulium Ln be selected from La, Nd, Pr, Sm, Yb, Tm, Gd, Dy (be preferably La, Nd, Sm,
Gd).
As preferably, catalyst S O
4 2-/ M
xO
y/ Ln
3+Be to use 10g M
xO
yWith 25ml concentration be the sulfuric acid of 0.5 ~ 2.5mol/L, the Ln of 0.001 ~ 0.1mol
2O
3Stir and to soak the 14h after-filtration that stagnates down, wash cl ions after gained behind retort furnace roasting 1～7h.
As preferably, catalyst levels is 3～9wt% of aminomethyl phenyl dialkoxy silicane in the step 1); The catalyst for cracking consumption is 0.05～10wt% of hydrolysing oil quality in the step 4).
Beneficial effect of the present invention
The present invention then with the hydrolysing oil catalytic cracking, obtains methyl-phenyl hybrid ring siloxane with the hydrolysis of rare-earth solid superacid catalysis aminomethyl phenyl dialkoxy silicane; Overcome and needed the washing neutralization among the existing preparation method; Labour intensity is big, produces the shortcoming that a large amount of spent acid waste water or product contain valency high metal ion content, and the preparation process cleans more; Labour intensity is low; Cracking temperature is lower, conserve energy, and also the methyl-phenyl hybrid ring siloxane of this method preparation does not contain trifunctional impurity, aminomethyl phenyl cyclotrisiloxane content is higher; Can be used for preparing high phenyl content, HV, HMW, not crosslinked, from the base polymer of the aminomethyl phenyl high temperature silicon rubber of levelling, and be used to prepare refractive index and be higher than 1.50 LED encapsulation and use organosilicon material.
Embodiment
The present invention can further specify through following embodiment, but embodiment is not the restriction to protection domain of the present invention.
Embodiment 1
1) in the clean there-necked flask of 10 L, adds 3kg aminomethyl phenyl diethoxy silane, 3kg deionized water, 150g rare-earth solid superacid SO
4 2-/ TiO
2/ La
3+, under mechanical stirring,, add the 2kg deionized water behind about 4h in 100 ℃ of following hydrolysis, continue under mechanical stirring in 100 ℃ of following hydrolysis, through measuring the refractive index of cut alcohol-water mixed liquid, judgement hydrolysis reaction terminal point.Through the 8h reaction, cut refractive index 1.3325 stops heating, with the reaction system standing demix approximately;
2) topple over upper aqueous layer, decompress filter is removed catalyst S O then
4 2-/ TiO
2/ La
3+
3) add about 1L toluene then, remove moisture with water trap under the normal pressure, obtain the colourless or light yellow hydrolysing oil of 1.94 kg;
4) add 5.8 g LiOH, under-0.096Mpa, heated up by room temperature gradually, receive 230 ℃-300 ℃ cut, can get the 1.80kg methyl-phenyl hybrid ring siloxane, product yield is 92.7%.
In dry 250ml there-necked flask, add 118g gained methyl-phenyl hybrid ring siloxane, 7g octamethylcyclotetrasiloxane, 0.2g vinyl double-seal head, 2.5g alkali glue, N
2Protection is warming up to 150 ℃ of thermal degradation catalyzer then down in 100 ℃ of following polyase 13 h, keeps the 1h decomposition catalyst, and 0.096MPa/200 ℃ is taken off low boiling then, obtains the vinyl base polymer of refractive index 1.5420.Be the methyl and phenyl hydrogen-containing silicon oil that 1.2:1 adds refractive index 1.5420 according to silicon hydrogen and silico ethylene base mol ratio then, organosilicon material, transmittance 96% are used in the LED encapsulation that can get refractive index 1.5420.
Embodiment 2
1) in the clean there-necked flask of 10 L, adds 3kg aminomethyl phenyl dimethoxy silane, 3kg deionized water, 150g rare-earth solid superacid SO
4 2-/ TiO
2/ Nd
3+, under mechanical stirring,, add the 1kg deionized water behind about 4h in 70 ℃ of following hydrolysis, continue under mechanical stirring in 70 ℃ of following hydrolysis, through measuring the refractive index of cut alcohol-water mixed liquid, judgement hydrolysis reaction terminal point.Through the 6h reaction, cut refractive index 1.3325 stops heating, with the reaction system standing demix approximately;
2) topple over upper aqueous layer, decompress filter is removed catalyst S O then
4 2-/ TiO
2/ Nd
3+
3) add about 1.5L toluene, remove moisture with water trap under the normal pressure, obtain the colourless or light yellow hydrolysing oil of 2.21kg;
4) add 6.64g LiOH, under-0.096Mpa, heat up by room temperature gradually, receive 230 ℃-310 ℃ cut, can get the 2.15kg methyl-phenyl hybrid ring siloxane, product yield 97.1%.
In dry 250ml there-necked flask, add 50.0g gained methyl-phenyl hybrid ring siloxane, the 100g octamethylcyclotetrasiloxane, 0.3g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane dewaters adding 3.0g alkali glue, N through 0.096MPa/30-40 ℃
2Protection is down in 100 ℃ of following polymerization 2h, is heated to 150 ℃ and keep the 1h decomposition catalyst then, takes off low boiling under 0.096MPa/180 ℃ then, obtains the methyl phenyl vinyl rubber of aminomethyl phenyl silica chain link 20% after the cooling.Recording cinnamic relatively number-average molecular weight through GPC is 6.85 * 10
5, MWD width 1.85.Get products therefrom 2g, place 25ml toluene, stirring at room 1h, product dissolves fully.Show that product can be used as aminomethyl phenyl elevated temperature heat sulfuration silicon rubber raw rubber.
Embodiment 3
1) in the clean there-necked flask of 10 L, adds 3kg aminomethyl phenyl dipropoxy silane, 4kg deionized water, 150g rare-earth solid superacid SO
4 2-/ Al
2O
3/ Sm
3+, under mechanical stirring,, add the 4kg deionized water behind about 4h in 110 ℃ of following hydrolysis, continue under mechanical stirring in 110 ℃ of following hydrolysis, through measuring the refractive index of cut alcohol-water mixed liquid, judgement hydrolysis reaction terminal point.Through the 8h reaction, cut refractive index 1.3325 stops heating, with the reaction system standing demix approximately;
2) topple over upper aqueous layer, decompress filter is removed catalyst S O then
4 2-/ Al
2O
3/ Y
3+
3) add about 2L toluene, remove moisture with water trap under the normal pressure, obtain the colourless or light yellow hydrolysing oil of 1.87kg;
4) add 9.4g LiOH, under-0.096Mpa, heat up by room temperature gradually, receive 230 ℃-310 ℃ cut, can get the 1.80kg methyl-phenyl hybrid ring siloxane, product yield 96.2%.
In dry 250ml there-necked flask, add 50.0g gained methyl-phenyl hybrid ring siloxane, the 100g octamethylcyclotetrasiloxane, 0.3g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane dewaters adding 3.0g alkali glue, N through 0.096MPa/30-40 ℃
2Protection is down in 100 ℃ of following polymerization 2h, is heated to 150 ℃ and keep the 1h decomposition catalyst then, takes off low boiling under 0.096MPa/180 ℃ then, obtains the methyl phenyl vinyl rubber of aminomethyl phenyl silica chain link 20% after the cooling.Recording cinnamic relatively number-average molecular weight through GPC is 7.20 * 10
5, MWD width 1.78.Get products therefrom 2g, place 25ml toluene, stirring at room 1h, product dissolves fully.Show that product can be used as aminomethyl phenyl elevated temperature heat sulfuration silicon rubber raw rubber.
Embodiment 4
1) in the clean there-necked flask of 10 L, adds 3kg aminomethyl phenyl diisopropoxy silane, 3kg deionized water, 150g rare-earth solid superacid SO
4 2-/ SiO
2/ Yb
3+, under mechanical stirring,, add the 3kg deionized water behind about 4h in 100 ℃ of following hydrolysis, continue under mechanical stirring in 100 ℃ of following hydrolysis, through measuring the refractive index of cut alcohol-water mixed liquid, judgement hydrolysis reaction terminal point.Through the 9h reaction, cut refractive index 1.3325 stops heating, with the reaction system standing demix approximately;
2) topple over upper aqueous layer, decompress filter is removed catalyst S O then
4 2-/ SiO
2/ Yb
3+
3) add about 1.5L toluene then, remove moisture with water trap under the normal pressure, obtain the colourless or light yellow hydrolysing oil of 1.87kg;
4) add 7.5 g LiOH then, under-0.096Mpa, heat up by room temperature gradually, receive 230 ℃-310 ℃ cut, can get the 1.78kg methyl-phenyl hybrid ring siloxane, product yield 95.1%.
Get 81.0g gained methyl-phenyl hybrid ring siloxane, 42g octamethylcyclotetrasiloxane, 0.2g vinyl double-seal head; 2.5g alkali glue; In 100 ℃ of following polymerizations, can get the transparent vinyl base silicone oil of refractive index 1.5140, be the methyl and phenyl hydrogen-containing silicon oil that 1.2:1 adds refractive index 1.5140 according to silicon hydrogen and silico ethylene base mol ratio then; Organosilicon material, transmittance 94% are used in the LED encapsulation that can obtain refractive index 1.5140.
Embodiment 5
1) in the clean there-necked flask of 10 L, adds 3kg aminomethyl phenyl diethoxy silane, 4kg deionized water, 150g rare-earth solid superacid SO
4 2-/ ZrO
2/ Gd
3+, under mechanical stirring,, add the 4kg deionized water behind about 4h in 100 ℃ of following hydrolysis, continue under mechanical stirring in 100 ℃ of following hydrolysis, through measuring the refractive index of cut alcohol-water mixed liquid, judgement hydrolysis reaction terminal point.Through the 12h reaction, cut refractive index 1.3325 stops heating, with the reaction system standing demix approximately;
2) topple over upper aqueous layer, decompress filter is removed catalyst S O then
4 2-/ ZrO
2/ Gd
3+
3) add about 1L toluene, remove moisture with water trap under the normal pressure, obtain the colourless or light yellow hydrolysing oil of 1.94 kg;
4) add 5.8 g LiOH, under-0.096Mpa, heated up by room temperature gradually, receive 230 ℃-300 ℃ cut, can get the 1.70kg methyl-phenyl hybrid ring siloxane, product yield is 87.6%.
Get 101g gained methyl-phenyl hybrid ring siloxane, 21.5g octamethylcyclotetrasiloxane, 0.2g vinyl double-seal head; 2.5g alkali glue; In 100 ℃ of following polymerizations, can get the transparent vinyl base silicone oil of refractive index 1.5235, be the methyl and phenyl hydrogen-containing silicon oil that 1.2:1 adds refractive index 1.5235 according to silicon hydrogen and silico ethylene base mol ratio then; Process the LED encapsulation of refractive index 1.5235 and use organosilicon material, transmittance 97%.
Claims (3)
1. the preparation method of a methyl-phenyl hybrid ring siloxane is characterized in that as follows:
1) aminomethyl phenyl dialkoxy silicane and catalyzer and deionized water are joined in the reactor drum of temperature control platinum probe, the reaction that under normal pressure and 60～130 ℃, is hydrolyzed receives alcohol-water mixture that reaction generates, the refractive index n of mensuration distillate
D 25, work as n
D 25Near 1.3325 o'clock, stop heating, cooling, standing demix; Wherein catalyst levels is 1～15wt% of aminomethyl phenyl dialkoxy silicane, and the mass ratio of aminomethyl phenyl dialkoxy silicane and deionized water is 1: 0.2～5;
Described aminomethyl phenyl dialkoxy silicane is one or more the mixture in aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dipropoxy silane, aminomethyl phenyl diisopropoxy silane, the aminomethyl phenyl dibutoxy silane;
Described catalyzer is for having general formula SO
4 2-/ M
xO
y/ Ln
3+Rare-earth solid superacid, M in the formula
xO
yBe TiO
2, Al
2O
3, SiO
2, ZrO
2In one or more mixture, thulium Ln is selected from La, Nd, Pr, Sm, Yb, Tm, Gd, Dy;
2) reaction mixture with standing demix separates, and solid super acid catalyst is removed through suction filtration by lower floor, obtains filtrating;
3) in gained filtrating, add the toluene of 0.2～5 times of filtrate volume, dewater, after the water Ex-all, steam and remove toluene, acquisition exsiccant hydrolysing oil with the water trap normal pressure;
4) in the dry hydrolysing oil of gained, add among catalyst for cracking LiOH or its hydrate, NaOH, KOH, RbOH, the CsOH one or more, under 200～320 ℃, 0.096MPa, carry out cracking, collect split product, promptly get methyl-phenyl hybrid ring siloxane; Wherein the catalyst for cracking consumption is 0.01～50wt% of hydrolysing oil quality.
2. preparation method according to claim 1 is characterized in that catalyst S O
4 2-/ M
xO
y/ Ln
3+Be to use 10g M
xO
yWith 25ml concentration be the sulfuric acid of 0.5～2.5mol/L, the Ln of 0.001～0.1mol
2O
3Stir dipping 14h after-filtration down, the washing cl ions is after gained behind retort furnace roasting 1～7h.
3. preparation method according to claim 1 and 2 is characterized in that catalyst levels is 3～9wt% of aminomethyl phenyl dialkoxy silicane in the step 1); The catalyst for cracking consumption is 0.05～10wt% of hydrolysing oil quality in the step 4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102390140A CN101935328B (en) | 2010-07-28 | 2010-07-28 | Preparation method of methyl phenyl mixed cyclosiloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102390140A CN101935328B (en) | 2010-07-28 | 2010-07-28 | Preparation method of methyl phenyl mixed cyclosiloxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101935328A CN101935328A (en) | 2011-01-05 |
| CN101935328B true CN101935328B (en) | 2012-06-20 |
Family
ID=43388922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102390140A Active CN101935328B (en) | 2010-07-28 | 2010-07-28 | Preparation method of methyl phenyl mixed cyclosiloxane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101935328B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018517688A (en) * | 2015-05-18 | 2018-07-05 | ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ | Cyclic siloxane compound and composition containing the same |
| CN104829646A (en) * | 2015-05-19 | 2015-08-12 | 湖北新蓝天新材料股份有限公司 | Methylphenylcyclosiloxane mixture and preparation method thereof |
| CN106432730B (en) * | 2016-09-21 | 2019-07-05 | 沈阳化工大学 | One kind containing Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link |
| CN107286347B (en) * | 2017-07-25 | 2023-03-17 | 广州硅芯材料科技有限公司 | Method for preparing phenyl hydrogen-containing silicone resin from methyl hydrogen-containing silicone oil |
| CN113980277A (en) * | 2020-07-27 | 2022-01-28 | 新特能源股份有限公司 | Phenyl hydroxyl silicone oil, phenyl hydrogen-containing silicone oil, and preparation methods and preparation devices thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343285A (en) * | 2008-08-28 | 2009-01-14 | 杭州师范大学 | Methyl-phenyl hybrid ring siloxane preparing method |
-
2010
- 2010-07-28 CN CN2010102390140A patent/CN101935328B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343285A (en) * | 2008-08-28 | 2009-01-14 | 杭州师范大学 | Methyl-phenyl hybrid ring siloxane preparing method |
Non-Patent Citations (2)
| Title |
|---|
| 杨秀利等.稀土固体超强酸SO42- /TiO2 /La3+催化合成丙酸环己酯.《榆林学院学报》.2009,第19卷(第6期),24-26、40. * |
| 罗蒙贤等.甲基苯基环硅氧烷的制备工艺研究.《研发前沿》.2008,第16卷(第13期),13-15. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101935328A (en) | 2011-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101935328B (en) | Preparation method of methyl phenyl mixed cyclosiloxane | |
| CN102643429B (en) | Method for preparing siloxane potassium alcoholate | |
| CN101935455B (en) | Organosilicon material for packaging LED and preparation method thereof | |
| CN103131189B (en) | Inorganic or organic hybridization nanocomposite for packaging light emitting diode (LED) and preparation method thereof | |
| CN102391529A (en) | Preparation method of silicone resin type organic/inorganic hybrid material for packaging | |
| CN101891893A (en) | Preparation method of phenyl-based hydrogen-based silicone resin for encapsulating LED | |
| CN104629057B (en) | A kind of methyl phenyl vinyl borosilicate resin, preparation method and its usage | |
| CN102181159A (en) | Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof | |
| CN102936414A (en) | High refraction and high adhesion large power LED packaging organosilicon material and preparation method thereof | |
| CN106478951A (en) | A kind of preparation method of LED packaging plastic methyl and phenyl hydrogen-containing silicon oil | |
| CN106008983A (en) | Silicon-boron tackifier and preparation method and application thereof | |
| CN103265703A (en) | High refractive index titanium hybrid silicon resin and preparation method thereof | |
| CN105801861B (en) | The method of organosilicon high-boiling product preparation superfines silicone resin | |
| CN103333276A (en) | Siloxane-group-containing long-wave-absorbing photoinitiator and preparation method thereof | |
| CN109880101A (en) | A kind of LED packaging plastic epoxidation modification phenyl polysiloxane and preparation method thereof | |
| CN104788488A (en) | Preparation method of naphthyl alkoxysilane | |
| CN104277222A (en) | Phenyl hydrogen-containing silicone resin for LED encapsulation and preparation method of phenyl hydrogen-containing silicone resin | |
| CN101850271B (en) | Platinum catalyst for olefin hydrosilylation, preparation method and application thereof | |
| CN101503422B (en) | Method for preparing methyl phenyl ring siloxane mixture | |
| CN105778100A (en) | Organosilicon tackifier and preparation method thereof and addition type silicone rubber composition | |
| US8158716B2 (en) | Preparation of hydrolyzable group-containing organohydrogenpolysiloxane and organopolysiloxane derived therefrom | |
| CN101343285B (en) | Methyl-phenyl hybrid ring siloxane preparing method | |
| CN108192083A (en) | Conjugated polymer containing trifluoromethyl and its preparation method and application | |
| US20140364639A1 (en) | Method for preparing trialkoxysilane | |
| CN102675358B (en) | Preparation method of methylphenyl-cyclosiloxane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201126 Address after: Room 1302, No. 373, Century Avenue, Nantong, Jiangsu Province, 226000 Patentee after: Jiangsu Jinshi Electric Power Design Co.,Ltd. Address before: 226300 No. 266 Century Avenue, hi tech Zone, Jiangsu, Nantong Patentee before: NANTONG WOTE OPTOELECTRONICS TECHNOLOGY Co.,Ltd. Effective date of registration: 20201126 Address after: 226300 No. 266 Century Avenue, hi tech Zone, Jiangsu, Nantong Patentee after: NANTONG WOTE OPTOELECTRONICS TECHNOLOGY Co.,Ltd. Address before: Hangzhou City, Zhejiang province 310036 Xihu District Wenyi Road No. 222 Hangzhou Normal University Laboratory silicone Patentee before: Hangzhou Normal University |
|
| TR01 | Transfer of patent right |