CN103450481A - Preparation method of methyl phenyl vinyl silicone - Google Patents
Preparation method of methyl phenyl vinyl silicone Download PDFInfo
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- CN103450481A CN103450481A CN2013104253052A CN201310425305A CN103450481A CN 103450481 A CN103450481 A CN 103450481A CN 2013104253052 A CN2013104253052 A CN 2013104253052A CN 201310425305 A CN201310425305 A CN 201310425305A CN 103450481 A CN103450481 A CN 103450481A
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Abstract
The invention discloses a preparation method of methyl phenyl vinyl silicone. The method comprises the following steps of: S10, first hydrolyzing a mixed monomer system containing trifunctional alkoxy silane, bifunctional alkoxy silane and vinyl end socket agent and obtaining a silanol mixed system; S20, then adding a basic catalyst into the mixed system in the step S10, and copolymerizing in the heating conditions to obtain the methyl phenyl vinyl silicone. The preparation method provided in the invention is high in reaction conversion ratio and easy in reaction conditions; the clean and transparent methyl phenyl vinyl silicone with single composition and type can be prepared thereby.
Description
Technical field
The present invention relates to the silicone resin technical field, be specifically related to a kind of preparation method of methyl phenyl vinyl polysiloxane.
Background technology
Methyl phenyl vinyl polysiloxane is one of principal item of silicone resin, because it has good electrical insulation properties and good anti-ozone, anti-corona, hydrophobic humidity resistance, also there is the good advantages such as chemical stability, be widely used in the aspects such as cosmetics of everyday use, electronics, machinery.Introduced phenyl in molecular chain due to methyl phenyl vinyl polysiloxane, make it there is resistance to elevated temperatures, radiation resistance, lubricity and the performance that mixes preferably, it demonstrates certain absorptivity to UV-light in addition, working temperature is-50 ℃～250 ℃, so it can be used as the liquid polymer host of cosmetics additive, lubricating oil additive, electronic package material etc.
Aminomethyl phenyl ethene silicone resin is the polysiloxane that part methyl is substituted by phenyl and end group is vinyl, and its structural formula is as shown in the formula shown in I, and wherein Ph is benzene ring substitution group, and Me is methyl, and Vi is vinyl.At present, the methyl phenyl vinyl polysiloxane of report all forms by vinyl chlorosilane and non-vinyl chlorosilane hydrolytie polycondensation both at home and abroad; But in this synthetic method, different proportioning raw materials and hydrolysising condition, resulting product composition, product kind are extremely complicated, cause stability and the poor controllability of product.
Summary of the invention
The product composition, the product kind complexity that the objective of the invention is to solve preparation method's existence of methyl phenyl vinyl polysiloxane in prior art cause the stability of product and the technical problem of poor controllability, and a kind of new preparation method is provided.
Particularly, the invention provides a kind of preparation method of methyl phenyl vinyl polysiloxane, comprise the following steps:
S10, the mix monomer system that first will contain trifunctional organoalkoxysilane, two functional alkoxysilanes and vinyl closure agent are hydrolyzed under acidic conditions, obtain the mixed system of silanol;
S20, then in the mixed system of step S10, add basic catalyst, carry out copolymerization under heating condition, obtain described methyl phenyl vinyl polysiloxane;
Described trifunctional organoalkoxysilane is directly to be connected with the silane of three alkoxyl groups on Siliciumatom; Described two functional alkoxysilanes are directly to be connected with the silane of two alkoxyl groups on Siliciumatom; Have at least on a Siliciumatom and directly be connected with phenyl in described trifunctional organoalkoxysilane, two functional alkoxysilanes, and have at least on a Siliciumatom and directly be connected with methyl in described trifunctional organoalkoxysilane, two functional alkoxysilanes; Described vinyl closure agent is many siloxanes that end group is vinyl.
As a further improvement on the present invention, in step S10, described trifunctional organoalkoxysilane is selected from one or more in phenyl trimethoxy silane, methyltrimethoxy silane, phenyl triethoxysilane, Union carbide A-162, vinyltriethoxysilane.
As a further improvement on the present invention, in step S10, described two functional alkoxysilanes are selected from aminomethyl phenyl dimethoxy silane, one or more in aminomethyl phenyl diethoxy silane, dimethoxydiphenylsilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl ethylene dimethoxy silane, methyl ethylene diethoxy silane.
As a further improvement on the present invention, in step S10, described vinyl closure agent is selected from one or more in tetramethyl divinyl disiloxane, trimethylammonium trivinyl cyclotrisiloxane, hexamethyl divinyl cyclotetrasiloxane, tetraphenyl tetrem thiazolinyl cyclotetrasiloxane, phenylbenzene six vinyl cyclotetrasiloxanes, triphenyl trivinyl cyclotrisiloxane.
As a further improvement on the present invention, in step S10, in described mix monomer system, the mol ratio of described phenyl and vinyl is (0.2～9): 1, and the mol ratio of phenyl and methyl is (0.2～5.5): 1.
As a further improvement on the present invention, in step S10, under described acidic conditions, hydrolysis is carried out under the condition that adopts an acidic catalyst; Described an acidic catalyst is selected from one or more in trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid; The temperature of described hydrolysis is 60～85 ℃.
As a further improvement on the present invention, in step S10, the consumption of described an acidic catalyst accounts for 0.05～0.1wt% of mix monomer system total mass.
As a further improvement on the present invention, in step S20, described basic catalyst is selected from one or more in potassium hydroxide, Tetramethylammonium hydroxide alkali glue, sodium hydroxide, lithium hydroxide, ammoniacal liquor, triethylamine, Trimethylamine 99, sodium ethylate, potassium ethylate, potassium tert.-butoxide.
As a further improvement on the present invention, in step S20, the consumption of described basic catalyst accounts for 0.1～0.5wt% of mix monomer system total mass.
As a further improvement on the present invention, in step S20, the condition of copolymerization comprises: temperature is 90～180 ℃, and the time is 1～16h.
As a further improvement on the present invention, also be included in after copolymerization completes the step that product is carried out to underpressure distillation.
The preparation method of methyl phenyl vinyl polysiloxane provided by the invention, by the kind to synthesis material and reaction conditions, suitably select, make the reaction conversion ratio of each raw material high, reaction conditions is easy, thereby prepare the methyl phenyl vinyl polysiloxane that clear, composition and kind are single, it has good high refractive index, high transmission rate, radiation hardness, high-low temperature resistant, weather resistance.Simultaneously, preparation method provided by the invention, raw material is easy to get, and technique is simple, easy and simple to handle, and mild condition is easy to control, and pollution-free, is convenient to industrialization.
The accompanying drawing explanation
The nmr spectrum that Fig. 1 is the ethyl methyl benzene thiazolinyl silicone resin for preparing of the embodiment of the present invention 1.
Embodiment
The invention provides a kind of preparation method of methyl phenyl vinyl polysiloxane, comprise the following steps:
S10, the mix monomer system that first will contain trifunctional organoalkoxysilane, two functional alkoxysilanes and vinyl closure agent are hydrolyzed under acidic conditions, obtain the mixed system of silanol;
S20, then in the mixed system of step S10, add basic catalyst, carry out copolymerization under heating condition, obtain described methyl phenyl vinyl polysiloxane;
Described trifunctional organoalkoxysilane is that the silane of three alkoxyl groups is arranged on Siliciumatom; Described two functional alkoxysilanes are that the silane of two alkoxyl groups is arranged on Siliciumatom; Have at least on a Siliciumatom and directly be connected with phenyl in described trifunctional organoalkoxysilane, two functional alkoxysilanes, and have at least on a Siliciumatom and directly be connected with methyl in described trifunctional organoalkoxysilane, two functional alkoxysilanes; Described vinyl closure agent is many siloxanes that end group is vinyl.
The preparation method of methyl phenyl vinyl polysiloxane provided by the invention, by the kind to synthesis material and reaction conditions, suitably select, make the reaction conversion ratio of each raw material high, reaction conditions is easy, thereby prepare the methyl phenyl vinyl polysiloxane that clear, composition and kind are single, it has good high refractive index, high transmission rate, radiation hardness, high-low temperature resistant, weather resistance.Simultaneously, preparation method provided by the invention, raw material is easy to get, and technique is simple, easy and simple to handle, and mild condition is easy to control, and pollution-free, is convenient to industrialization.
Particularly, in step S10, described trifunctional organoalkoxysilane is directly to be connected with the silane of three alkoxyl groups on Siliciumatom.Therefore, described trifunctional organoalkoxysilane is under hydrolysising condition, and on Siliciumatom, direct-connected three alkoxyl groups are hydrolyzed and form the silanol structure, obtain the silanol with three hydroxy functional groups, i.e. the trifunctional silanol.In the present invention, described trifunctional organoalkoxysilane can be selected from one or more in phenyl trimethoxy silane, methyltrimethoxy silane, phenyl triethoxysilane, Union carbide A-162, vinyltriethoxysilane, but is not limited to this.More preferably, in situation, described trifunctional organoalkoxysilane is selected from phenyltrimethoxysila,e.
Described two functional alkoxysilanes are that the silane of two alkoxyl groups is directly arranged on Siliciumatom, so it is under hydrolysising condition, and two alkoxyl groups are hydrolyzed and form the silanol structure, obtain the silanol that contains two hydroxyls, i.e. two functional group's silanols.Under preferable case, described two functional alkoxysilanes are selected from one or more in aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, dimethoxydiphenylsilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl ethylene dimethoxy silane, methyl ethylene diethoxy silane, but are not limited to this.More preferably, in situation, described two functional alkoxysilanes are selected from one or more in dimethyldimethoxysil,ne, aminomethyl phenyl dimethoxy silane or phenylbenzene dimethoxy alkane.
That, in the present invention, the functional number in described trifunctional organoalkoxysilane, two functional alkoxysilanes is all for the number of alkoxyl group with it may be noted that.And be to guarantee that mix monomer system provided by the invention in the end can prepare described methyl phenyl vinyl polysiloxane, therefore have at least on a Siliciumatom in described trifunctional organoalkoxysilane, two functional alkoxysilanes and directly be connected with phenyl, and have at least on a Siliciumatom and directly be connected with methyl in described trifunctional organoalkoxysilane, two functional alkoxysilanes.Those skilled in the art can do following understanding, (1) while adopting phenyl trifunctional organoalkoxysilane in the trifunctional organoalkoxysilane, described two functional alkoxysilanes must employing at least contain two functional alkoxysilanes of a methyl, such as adopting other substituting group dialkoxy silicane of dimethyl dialkoxy silicane or monomethyl (including, but not limited to aminomethyl phenyl dialkoxy silicane, methyl ethylene dialkoxy silicane, methylethyl dialkoxy silicane etc.).(2) similarly, while adopting methyl trifunctional organoalkoxysilane in the trifunctional organoalkoxysilane, described two functional alkoxysilanes must employing at least contain two functional alkoxysilanes of a phenyl, such as adopting other substituting group dialkoxy silicane of phenylbenzene dialkoxy silicane or single phenyl (including, but not limited to aminomethyl phenyl dialkoxy silicane, phenyl vinyl dialkoxy silicane, phenylethyl dialkoxy silicane etc.).(3) for example, while adopting non-phenyl and methyl substituted other trifunctional organoalkoxysilane (vinyl trialkyl oxysilane, ethyl trialkoxy silane) in the trifunctional organoalkoxysilane, now on the Siliciumatom of described two functional alkoxysilanes, must contain methyl and phenyl simultaneously, now described two functional alkoxysilanes can only be selected the aminomethyl phenyl dialkoxy silicane, can be for example aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane etc.
Described vinyl closure agent is many siloxanes that end group is vinyl.In the present invention, as without particular determination, described many siloxanes refer to that the Siliciumatom number is the siloxanes more than 2.Accordingly, described vinyl closure agent is under hydrolysising condition, and the silica group in its structure also can corresponding hydrolysis form the silanol structure, thereby obtains the vinyl silanol.Under preferable case, in the present invention, described vinyl closure agent is selected from one or more in tetramethyl divinyl disiloxane, trimethylammonium trivinyl cyclotrisiloxane, hexamethyl divinyl cyclotetrasiloxane, tetraphenyl tetrem thiazolinyl cyclotetrasiloxane, phenylbenzene six vinyl cyclotetrasiloxanes, triphenyl trivinyl cyclotrisiloxane.More preferably, in situation, described vinyl closure agent is tetramethyl divinyl disiloxane.
In the present invention, there is no particular requirement for the content of phenyl, methyl and vinyl in reaction system (being the mix monomer system), as long as it can meet the actual production demand of the methyl phenyl vinyl polysiloxane finally made.Under preferable case, in described mix monomer system, the mol ratio of phenyl and vinyl is (0.2～9): 1, and the mol ratio of phenyl and methyl is (0.2～5.5): 1.
In the present invention, under described acidic conditions, hydrolysis is carried out under the condition that adopts an acidic catalyst.Wherein, described an acidic catalyst can adopt strong acid type liquid, for example can be selected from one or more in trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid, preferably adopts the vitriol oil.The temperature of described hydrolysis is 60～85 ℃.
As a kind of preferred implementation of the present invention, for ease of fully carrying out of the hydrolysis of trifunctional organoalkoxysilane, two functional silicone silane and vinyl closure agent, described hydrolysis reaction carries out in solvent.The solvent adopted can, for various silane commonly used in prior art, the good solvent of siloxanes, for example can adopt toluene, water, but be not limited to this.
Described an acidic catalyst is mainly the carrying out of facilitation of hydrolysis reaction, and its consumption is without too much.Under preferable case, the consumption of an acidic catalyst accounts for 0.05～0.1wt% of mix monomer system total mass.
Following trifunctional organoalkoxysilane be take the phenyl trialkoxy silane as example, two functional silicones be take the dimethyl dialkoxy silicane as example, the vinyl closure agent be take tetramethyl divinyl disiloxane as example, and its reaction mechanism that is hydrolyzed respectively generation trifunctional silanol, two functional group's silanols, vinyl silanol is as shown in the formula shown in II:
Wherein, Ph is the phenyl ring group, is (a) the trifunctional silanol, is (b) two functional group's silanols, (c) is the vinyl silanol.
According to preparation method provided by the invention, after first the mix monomer system being hydrolyzed into to the mixed system that contains corresponding silanol separately, then add basic catalyst, make each silanol carry out copolymerization under alkaline condition, can obtain described methyl phenyl vinyl polysiloxane.
Take above-mentioned (a) and (b), (c) is example, shown in its following formula III of copolymerization mechanism under alkaline condition:
In the present invention, described basic catalyst can adopt various organic basic catalyzer or inorganic alkaline catalyst common in prior art, for example can be selected from one or more in potassium hydroxide, Tetramethylammonium hydroxide alkali glue, sodium hydroxide, lithium hydroxide, ammoniacal liquor, triethylamine, Trimethylamine 99, sodium ethylate, potassium ethylate, potassium tert.-butoxide, preferably adopt Tetramethylammonium hydroxide alkali glue, but be not limited to this.Under preferable case, the consumption of basic catalyst accounts for 0.1～0.5wt% of mix monomer system total mass.
Common practise as those skilled in the art, for preventing that basic catalyst from reacting and causing the consumption of basic catalyst too much with an acidic catalyst residual in hydrolysis reaction system, also can be before adding basic catalyst the step of an acidic catalyst in first removal system.The step of removing an acidic catalyst can be extraction, but is not limited to this.
In the present invention, the condition of described copolymerization comprises: temperature is 90～180 ℃, and the time is 1～16h.Under preferable case, the condition of described copolymerization comprises: temperature is 110～140 ℃, and the time is 3～14h.
As a kind of preferred implementation of the present invention, also be included in after copolymerization completes the step that product is carried out to underpressure distillation.The effect of underpressure distillation is mainly to remove in the product system to have neither part nor lot in reaction or unreacted small molecules thing completely, to obtain the methyl phenyl vinyl polysiloxane that purity is higher.Under preferable case, described underpressure distillation is for-0.096MPa, temperature, to be to carry out under 170 ℃ at pressure.
Adopt preparation method provided by the invention, the ethyl methyl benzene thiazolinyl silicone resin prepared, it has structure shown in formula I, product composition is clear, kind is single, its number-average molecular weight is 2000～7500, and specific refractory power is 1.45～1.60, and contents of ethylene is 0.2～1.2wt%, there is radiation hardness, high-low temperature resistant, the advantage such as weather-proof, be applicable to the host of electron pouring sealant and sealing-ring with lubricator.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with specific embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.Embodiment is that in Comparative Examples, the raw material that adopts all is commercially available, and the present invention is not particularly limited.
Embodiment 1
At 2L with dropping funnel, prolong, add 200g toluene in the there-necked flask of thermometer, 100g water and 50g tetramethyl divinyl disiloxane, add the 0.5g vitriol oil to stir and be warming up to 65～75 ℃ of reaction 1.5h, slowly splash into the 415.8g phenyltrimethoxysila,e, the 20g dimethyldimethoxysil,ne (is mol ratio phenyl: vinyl=8:1, mol ratio phenyl: methyl=2:1), in 1 hour, dropwise, under 70 ℃ of conditions, reflux 1 hour, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 5 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain the water white transparency semi-solid product, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.5450, product yield is 85～90%, adopt polystyrene as standard substance, recording its number-average molecular weight by gel chromatography is 7000.
The methyl phenyl vinyl polysiloxane obtained is dissolved in to deuterated reagent CDCl
3in, adopt tetramethylsilane (CH
3)
4si is standard substance, and the molecular structure nmr spectrum of the methyl phenyl vinyl polysiloxane that utilizes nucleus magnetic resonance 1H-NMR to record as shown in Figure 1, is extrapolated its architecture formula and is:
(Me
2siO
2/2)
0.1(PhSiO
3/2)
0.8(Me
2viSiO
1/2)
0.1, be designated as molar content under in formula.
Embodiment 2
At 2L with dropping funnel, prolong, add 250g toluene in the there-necked flask of thermometer, 91g water and 50g tetramethyl divinyl disiloxane, add the 0.5g vitriol oil, stirring is warming up to 65～75 ℃ of reaction 2h, slowly splash into the 415.8g phenyltrimethoxysila,e, 70g aminomethyl phenyl dimethoxy silane and 50g dimethyldimethoxysil,ne (are mol ratio phenyl: vinyl=8:1, mol ratio phenyl: methyl=1.6:1), in 1 hour, dropwise, under 80 ℃ of conditions, reflux 1 hour, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 5 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain colourless semi-solid opaque products, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.5430, product yield is 90～95%, adopt polystyrene as standard substance, recording its number-average molecular weight by gel chromatography is 4800.
Adopt the testing method identical with embodiment 1 to utilize nucleus magnetic resonance to be detected to the methyl phenyl vinyl polysiloxane of the present embodiment, infer that its structural formula is:
(PhSiO
3/2)
0.7(MePhSiO
2/2)
0.1(Me
2siO
2/2)
0.1(Me
2viSiO
1/2)
0.1, be designated as molar content under in formula.
Embodiment 3
At 2L with dropping funnel, prolong, add 230g toluene in the there-necked flask of thermometer, 91g water, 0.5g the vitriol oil, the 50g tetramethyl divinyl disiloxane, stirring is warming up to 65～75 ℃ of reaction 2h, slowly splash into the 280g phenyltrimethoxysila,e and 120g aminomethyl phenyl dimethoxy silane (is mol ratio phenyl: vinyl=9:1, mol ratio phenyl: methyl=1.8:1), in 1 hour, dropwise, under 80 ℃ of conditions, reflux 2 hours, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 8 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain the water white transparency product, 25 ℃ of viscosity are 2000CPS, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.5250, product yield is 80～85%, adopt polystyrene as standard substance, recording its number-average molecular weight by gel chromatography is 3590.
Adopt the testing method identical with embodiment 1 to utilize nucleus magnetic resonance to be detected to the methyl phenyl vinyl polysiloxane of the present embodiment, infer that its structural formula is:
(PhSiO
3/2)
0.6(MePhSiO
2/2)
0.3(Me
2viSiO
1/2)
0.1, be designated as molar content under in formula.
Embodiment 4
At 2L with dropping funnel, prolong, add 200g toluene in the there-necked flask of thermometer, 91g water and 50g tetramethyl divinyl disiloxane, add the 0.5g vitriol oil, stirring is warming up to 65～75 ℃ of reaction 1.5h, slowly splash into the 30g phenyltrimethoxysila,e, 168g aminomethyl phenyl dimethoxy silane and 10g dimethyldimethoxysil,ne (are mol ratio phenyl: vinyl=3.5:1, mol ratio phenyl: methyl=0.682:1), in 1 hour, dropwise, under 70 ℃ of conditions, reflux 2 hours, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 8 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain the water white transparency product, 25 ℃ of viscosity are 6000CPS, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.5350, product yield is 85～90%, adopt polystyrene as standard substance, recording its number-average molecular weight by gel chromatography is 4000.
Adopt the testing method identical with embodiment 1 to utilize nucleus magnetic resonance to be detected to the methyl phenyl vinyl polysiloxane of the present embodiment, infer that its structural formula is:
(PhSiO
3/2)
0.15(MePhSiO
2/2)
0.6(Me
2siO
2/2)
0.05(Me
2viSiO
1/2)
0.2, be designated as molar content under in formula.
Embodiment 5
At 2L with dropping funnel, prolong, add the 170g phenyltrimethoxysila,e in the there-necked flask of thermometer, 120g aminomethyl phenyl dimethoxy silane and 10g dimethyldimethoxysil,ne, add the 0.5g vitriol oil to stir and be warming up to 65～75 ℃ of reaction 1.5h, slowly splash into 200g toluene, 91g water and 50g tetramethyl divinyl disiloxane (are mol ratio phenyl: vinyl=3.03:1, mol ratio phenyl: methyl=1.65:1), in 1 hour, dropwise, under 70 ℃ of conditions, reflux 1 hour, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 8 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain the water white transparency semi-solid product, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.5440, product yield is 80～85%, adopt polystyrene as standard substance, recording its number-average molecular weight by gel chromatography is 5100.
Adopt the testing method identical with embodiment 1 to utilize nucleus magnetic resonance to be detected to the methyl phenyl vinyl polysiloxane of the present embodiment, infer that its structural formula is:
(PhSiO
3/2)
0.54(MePhSiO
2/2)
0.37(Me
2siO
2/2)
0.06(Me
2viSiO
1/2)
0.03, be designated as molar content under in formula.
Embodiment 6
At 2L with dropping funnel, prolong, add 250g toluene in the there-necked flask of thermometer, 91g water and 30g tetramethyl divinyl disiloxane, add the 0.5g vitriol oil to stir and be warming up to 65～75 ℃ of reaction 1.5h, slowly splash into the 170g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane and 30g dimethyldimethoxysil,ne (are mol ratio phenyl: vinyl=8.6:1, mol ratio phenyl: methyl=1.78:1), in 1 hour, dropwise, under 85 ℃ of conditions, reflux 1 hour, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 5 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain the water white transparency product, 25 ℃ of viscosity are 6000cps, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.5500, product yield is 80～85%, adopt polystyrene as standard substance, recording its number-average molecular weight by gel chromatography is 7200.
Adopt the testing method identical with embodiment 1 to utilize nucleus magnetic resonance to be detected to the methyl phenyl vinyl polysiloxane of the present embodiment, infer that its structural formula is:
(PhSiO
3/2)
0.6(Ph
2siO
2/2)
0.13(Me
2siO
2/2)
0.17(Me
2viSiO
1/2)
0.1, be designated as molar content under in formula.
Embodiment 7
At 2L with dropping funnel, prolong, add 250g toluene in the there-necked flask of thermometer, 91g water and 45g tetramethyl divinyl disiloxane, add the 0.5g vitriol oil to stir and be warming up to 65～75 ℃ of reaction 1.5h, slowly splash into the 170g phenyltrimethoxysila,e and 120g aminomethyl phenyl dimethoxy silane (is mol ratio phenyl: vinyl=9:1, mol ratio phenyl: methyl=1.5:1), in 1 hour, dropwise, under 85 ℃ of conditions, reflux 1 hour, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 5 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain the water white transparency product, 25 ℃ of viscosity are 120000cps, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.5450, product yield is 85～90%, adopt polystyrene as standard substance, recording its number-average molecular weight by gel chromatography is 6100 for recording its number-average molecular weight.
Adopt the testing method identical with embodiment 1 to utilize nucleus magnetic resonance to be detected to the methyl phenyl vinyl polysiloxane of the present embodiment, infer that its structural formula is:
(PhSiO
3/2)
0.5(MePhSiO
2/2)
0.4(Me
2viSiO
3/2)
0.1, be designated as molar content under in formula.
Embodiment 8
At 2L with dropping funnel, prolong, add 250g toluene in the there-necked flask of thermometer, 91g water and 45g tetramethyl divinyl disiloxane, add the 0.5g vitriol oil to stir and be warming up to 65～75 ℃ of reaction 1.5h, slowly splashing into 198.2g phenyltrimethoxysila,e and 48.8g dimethoxydiphenylsilane (is mol ratio phenyl: vinyl=6.125:1, mol ratio phenyl: methyl=3.06:1), in 1 hour, dropwise, under 85 ℃ of conditions, reflux 1 hour, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 5 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain the water white transparency product, 25 ℃ of viscosity are 3000cps, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.5440, product yield is 85～90%, adopt polystyrene as standard substance, recording its number-average molecular weight by gel chromatography is 4500 for recording its number-average molecular weight.
Adopt the testing method identical with embodiment 1 to utilize nucleus magnetic resonance to be detected to the methyl phenyl vinyl polysiloxane of the present embodiment, infer that its structural formula is:
(PhSiO
3/2)
0.7(Ph
2siO
2/2)
0.14(Me
2viSiO
1/2)
0.16, be designated as molar content under in formula.
Embodiment 9
At 2L with dropping funnel, prolong, add 250g toluene in the there-necked flask of thermometer, 91g water and 60g tetramethyl divinyl disiloxane, add the 1g vitriol oil to stir and be warming up to 65～75 ℃ of reaction 1.5h, slowly splash into the 170g phenyltrimethoxysila,e, the 40g dimethoxydiphenylsilane, the 30g dimethyldimethoxysil,ne (is mol ratio phenyl: vinyl=3.7:1, mol ratio phenyl: methyl=1.03:1), in 1 hour, dropwise, under 85 ℃ of conditions, reflux 1 hour, add water and toluene extraction minute water-yielding stratum, till arriving neutrality, add 1g Tetramethylammonium hydroxide alkali glue, under 125 ℃ of conditions, reflux 5 hours, after having reacted, underpressure distillation desolventizes,-0.096MPa, temperature is to distill 3h under 170 ℃, be cooled to room temperature, obtain the water white transparency product, 25 ℃ of viscosity are 80000cps, obtain the methyl phenyl vinyl polysiloxane of the present embodiment, its refractive index is 1.54500, product yield is 85～90%, recording its number-average molecular weight by gel chromatography is 5000 for recording its number-average molecular weight.
Adopt the testing method identical with embodiment 1 to utilize nucleus magnetic resonance to be detected to the methyl phenyl vinyl polysiloxane of the present embodiment, infer that its structural formula is:
(PhSiO
3/2)
0.54(Ph
2siO
2/2)
0.10(Me
2siO
2/2)
0.16(Me
2viSiO
1/2)
0.2, be designated as molar content under in formula.
From embodiment 1-9 can find out, adopt preparation method provided by the invention, prepare methyl phenyl vinyl polysiloxane, product yield is 85～90%, and the product structure composition is clear, kind is single, specific refractory power is 1.45～1.60, has radiation hardness, high-low temperature resistant, the advantage such as weather-proof, is applicable to the host of electron pouring sealant and sealing-ring with lubricator.And the product yield for preparing methyl phenyl vinyl polysiloxane by vinyl chlorosilane and non-vinyl chlorosilane hydrolytie polycondensation in prior art is only 50～60%, and product composition, kind are extremely complicated.
Above embodiment is only the preferred embodiment of the present invention, it should be pointed out that to those skilled in the art, and under the premise without departing from the principles of the invention, some improvement of having done, also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a methyl phenyl vinyl polysiloxane, is characterized in that, comprises the following steps:
S10, the mix monomer system that first will contain trifunctional organoalkoxysilane, two functional alkoxysilanes and vinyl closure agent are hydrolyzed under acidic conditions, obtain the mixed system of silanol;
S20, then in the mixed system of step S10, add basic catalyst, carry out copolymerization under heating condition, obtain described methyl phenyl vinyl polysiloxane;
Described trifunctional organoalkoxysilane is directly to be connected with the silane of three alkoxyl groups on Siliciumatom; Described two functional alkoxysilanes are directly to be connected with the silane of two alkoxyl groups on Siliciumatom; Have at least on a Siliciumatom and directly be connected with phenyl in described trifunctional organoalkoxysilane, two functional alkoxysilanes, and have at least on a Siliciumatom and directly be connected with methyl in described trifunctional organoalkoxysilane, two functional alkoxysilanes; Described vinyl closure agent is many siloxanes that end group is vinyl.
2. preparation method according to claim 1, it is characterized in that: in step S10, described trifunctional organoalkoxysilane is selected from one or more in phenyl trimethoxy silane, methyltrimethoxy silane, phenyl triethoxysilane, Union carbide A-162, vinyltriethoxysilane.
3. preparation method according to claim 1, it is characterized in that: in step S10, described two functional alkoxysilanes are selected from aminomethyl phenyl dimethoxy silane, one or more in aminomethyl phenyl diethoxy silane, dimethoxydiphenylsilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl ethylene dimethoxy silane, methyl ethylene diethoxy silane.
4. preparation method according to claim 1, it is characterized in that: in step S10, described vinyl closure agent is selected from one or more in tetramethyl divinyl disiloxane, trimethylammonium trivinyl cyclotrisiloxane, hexamethyl divinyl cyclotetrasiloxane, tetraphenyl tetrem thiazolinyl cyclotetrasiloxane, phenylbenzene six vinyl cyclotetrasiloxanes, triphenyl trivinyl cyclotrisiloxane.
5. according to the described preparation method of claim 1-4 any one, it is characterized in that: in step S10, in described mix monomer system, the mol ratio of phenyl and vinyl is (0.2 ~ 9): 1, and the mol ratio of phenyl and methyl is (0.2 ~ 5.5): 1.
6. according to the described preparation method of claim 1-4 any one, it is characterized in that: in step S10, under described acidic conditions, hydrolysis is carried out under the condition that adopts an acidic catalyst; Described an acidic catalyst is selected from one or more in trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid; The temperature of described hydrolysis is 60 ~ 85 ℃.
7. preparation method according to claim 6, it is characterized in that: in step S10, the consumption of described an acidic catalyst accounts for 0.05 ~ 0.5wt% of mix monomer system total mass.
8. preparation method according to claim 1, it is characterized in that: in step S20, described basic catalyst is selected from one or more in potassium hydroxide, Tetramethylammonium hydroxide alkali glue, sodium hydroxide, lithium hydroxide, ammoniacal liquor, triethylamine, Trimethylamine 99, sodium ethylate, potassium ethylate, potassium tert.-butoxide.
9. preparation method according to claim 6, it is characterized in that: in step S20, the consumption of described basic catalyst accounts for 0.1 ~ 0.5wt% of mix monomer system total mass, and the condition of described copolymerization comprises: temperature is 90 ~ 180 ℃, and the time is 1 ~ 16h.
10. preparation method according to claim 1 is characterized in that: the step of after also being included in copolymerization and completing, product being carried out to underpressure distillation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937445A (en) * | 2014-03-24 | 2014-07-23 | 上海大学 | Preparation method of transparent organic silica gel with high refractive index for high brightness and large power COB-LED encapsulation |
| CN104892940A (en) * | 2014-03-05 | 2015-09-09 | 马凤国 | Preparation method for siloxane |
| CN108003347A (en) * | 2017-11-23 | 2018-05-08 | 烟台德邦先进硅材料有限公司 | A kind of preparation method for high-power encapsulation MDT silicones |
| CN109796931A (en) * | 2017-11-16 | 2019-05-24 | 北京科化新材料科技有限公司 | Silicon resin composition and its application and LED encapsulation material |
| CN110408031A (en) * | 2019-07-12 | 2019-11-05 | 湖北大学 | Active branching carbon silane with multiterminal functional group and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381459A (en) * | 2008-10-23 | 2009-03-11 | 上海树脂厂有限公司 | Production process of high viscosity phenylmethylvinyl silicone rubber |
| CN101717512A (en) * | 2009-11-20 | 2010-06-02 | 苏州大学 | Method for preparing methyl phenyl vinyl silicone resin |
| CN103012797A (en) * | 2012-11-23 | 2013-04-03 | 广东聚合有机硅材料有限公司 | Preparation method of methyl phenyl vinyl silicone oil |
| CN103012798A (en) * | 2012-11-23 | 2013-04-03 | 广东聚合有机硅材料有限公司 | Preparation method of methyl phenyl vinyl silicone resin |
-
2013
- 2013-09-17 CN CN2013104253052A patent/CN103450481A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381459A (en) * | 2008-10-23 | 2009-03-11 | 上海树脂厂有限公司 | Production process of high viscosity phenylmethylvinyl silicone rubber |
| CN101717512A (en) * | 2009-11-20 | 2010-06-02 | 苏州大学 | Method for preparing methyl phenyl vinyl silicone resin |
| CN103012797A (en) * | 2012-11-23 | 2013-04-03 | 广东聚合有机硅材料有限公司 | Preparation method of methyl phenyl vinyl silicone oil |
| CN103012798A (en) * | 2012-11-23 | 2013-04-03 | 广东聚合有机硅材料有限公司 | Preparation method of methyl phenyl vinyl silicone resin |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892940A (en) * | 2014-03-05 | 2015-09-09 | 马凤国 | Preparation method for siloxane |
| CN103937445A (en) * | 2014-03-24 | 2014-07-23 | 上海大学 | Preparation method of transparent organic silica gel with high refractive index for high brightness and large power COB-LED encapsulation |
| CN103937445B (en) * | 2014-03-24 | 2017-02-08 | 上海大学 | Preparation method of transparent organic silica gel with high refractive index for high brightness and large power COB-LED encapsulation |
| CN109796931A (en) * | 2017-11-16 | 2019-05-24 | 北京科化新材料科技有限公司 | Silicon resin composition and its application and LED encapsulation material |
| CN108003347A (en) * | 2017-11-23 | 2018-05-08 | 烟台德邦先进硅材料有限公司 | A kind of preparation method for high-power encapsulation MDT silicones |
| CN110408031A (en) * | 2019-07-12 | 2019-11-05 | 湖北大学 | Active branching carbon silane with multiterminal functional group and preparation method thereof |
| CN111040168A (en) * | 2019-12-26 | 2020-04-21 | 广东盈骅新材料科技有限公司 | Epoxy modified organic silicon resin and preparation method thereof |
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