CN105315468A - Epoxy polysiloxane and epoxidation preparation method thereof - Google Patents
Epoxy polysiloxane and epoxidation preparation method thereof Download PDFInfo
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Abstract
The invention discloses epoxy polysiloxane and an epoxidation preparation method thereof. The method comprises the steps that firstly, octamethylcyclotetrasiloxane, 2,4,6,8-Tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane and vinyl dual end sockets are used for negative ion loop opening on the alkaline condition to obtain a basic material, and then a mixture obtained by mixing a tetracarboxylic acid metal phthalocyanine complex and H2O2 is used as a catalyst in the presence of ethyl acetate to obtain the epoxy polysiloxane compound. The preparation method is simple, the interface compatibility caused by blending modification is avoided, the defects that the number of copolymerization modification side reactions is large and the catalyst is hard to remove are overcome, and the obtained compound can be used in the technical field of LED illuminating lamps.
Description
Technical field
The present invention relates to macromolecule synthesising technology field, be specifically related to a kind of epoxy polysiloxane and epoxidation preparation method thereof.
Background technology
Photodiode (LED) has been widely used in the fields such as picture and text showing, traffic signals, detector system, electronics, backlight.In recent years, along with power-type LED is popularized, especially based on the development of the white light LEDs of ultraviolet, while requiring packaged material to have higher absorption to UV-light, it can be kept at visible region high transparent; In addition, the development of LED technology, diversified needs are created to brightness, purposes, packaged type etc., adopt epoxy resin and the mutual modification of polysiloxane, due in structure simultaneously containing organosilicon composition and epoxy component, the advantage of the electrical insulation capability of the good mechanical property of epoxy resin, adhesiveproperties and excellence and silicone resin high-low temperature resistant, protection against the tide, excellent weathering resistance and electrical insulation capability can be given full play to.
Traditional modifying epoxy resin by organosilicon generally adopts blending and modifying or modification by copolymerization.Blending and modifying first organosilicon and epoxy resin is mixed, then in mixed system, add the curing moldings such as solidifying agent, curing catalyst and other additives.But the two solubility parameters difference is comparatively large, is easily separated.And the performance of blend is relevant with the morphological structure of blend, morphological structure is determined by each component compatibility of co-mixing system, and the compatibility problem both therefore solving is crucial.Modification by copolymerization is consistency in order to improve organosilicon material and epoxy resin and utilizes hydroxyl and the epoxy reaction of active group on organosilicon and epoxy resin, more stablize because introduce in the structure of cured product and there is flexible Si-O-Si segment, but reacting wayward and catalyzer difficulty is removed and affected product property.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of epoxy polysiloxane and epoxidation preparation method thereof.In the inventive method, by carrying out epoxidation to the carbon-carbon double bond on polysiloxane, thus obtain modifying epoxy resin by organosilicon, this method reaction temperature and, used catalyst is metal complex pressed powder and H
2o
2, easily separated and removal.Avoid the interface compatibility problem that blending and modifying causes, and modification by copolymerization side reaction is many, the shortcomings such as the difficult removal of catalyzer.
Technical scheme of the present invention is specifically described as follows.
The invention provides a kind of epoxy polysiloxane compound, the transmittance of this compound is between 90 ~ 95%, and the viscosity at room temperature 25 DEG C is between 4000 ~ 7000mPa.s; Its structural formula is as follows:
Wherein, x represents the polymerization degree, and span is 20-30.
The present invention also provides a kind of epoxidation preparation method of above-mentioned epoxy polysiloxane compound, and concrete steps are as follows:
(1) preparation of many vinyl polysiloxane
By octamethylcyclotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane and vinyl double-seal head, (chemical name is 1,3 one divinyl 1,1,3,3 one tetramethyl disiloxanes) according to 30:(5-15): the mass ratio of (0.2-0.8), at reduced pressure, dewater 0.5h ~ 1h at 40 DEG C ~ 80 DEG C temperature; Add catalyzer tetramethylammonium hydroxide aqueous solution afterwards, at 90 DEG C ~ 110 DEG C temperature, react 4h ~ 8h, reaction terminates rear decomposition catalyst and removes low-boiling-point substance, obtains many vinyl polysiloxane; Wherein, the add-on of Tetramethylammonium hydroxide accounts for 0.03% ~ 0.05% of mix monomer total mass; The structural formula of described many vinyl polysiloxane is as follows:
(2) preparation of epoxy polysiloxane compound
Many vinyl polysiloxane that step (1) prepares are added drop-wise in the solution containing epoxidation reagent, at 30 DEG C ~ 70 DEG C temperature, reaction 3h ~ 6h, purifies and separates obtains epoxy polysiloxane afterwards; Wherein: epoxidation reagent is tetracarboxylic metal phthalocyanine complex compound and 30wt%H
2o
2mixture; Tetracarboxylic metal phthalocyanine complex compound and 30wt%H
2o
2mass ratio be 1:3-1:10; The mass ratio of many vinyl polysiloxane and tetracarboxylic metal phthalocyanine complex compound is 10:2-10:6, and the structural formula of described epoxy polysiloxane is as follows:
In above-mentioned steps (1), the mass ratio of octamethylcyclotetrasiloxane and t etram-ethyltetravinylcyclotetrasiloxane, vinyl double-seal head is 30:(8-12): (0.3-0.6).
In above-mentioned steps (1), dewater at 50 DEG C ~ 70 DEG C temperature.
In above-mentioned steps (2), temperature is 40 DEG C ~ 60 DEG C, and the mass ratio of many vinyl polysiloxane and tetracarboxylic metal phthalocyanine complex compound is 10:4.
In above-mentioned steps (2), described containing in the solution of epoxidation reagent, solvent is ethyl acetate or methyl-sulphoxide.
In above-mentioned steps (2), described containing in the solution of epoxidation reagent, the mass volume ratio of epoxidation reagent and solvent is 1:4-1:10mg/mL.
In above-mentioned steps (2), the purifying of epoxy polysiloxane is by first filtering, and the mode of then underpressure distillation realizes.The condition of underpressure distillation is under-0.095MPa, 40 DEG C ~ 70 DEG C.
The NDJ-1 rotational viscosimeter that the viscosity of the epoxy polysiloxane of gained of the present invention adopts Shanghai sharp bearing device Manufacturing Co., Ltd to provide, pass through GB/T2794-2013, " the mensuration list cylinder rotary viscosimeter method of tackiness agent viscosity ", detect under the condition of room temperature 25 DEG C, its viscosity is 4000 ~ 7000mPa.s.Adopt the UV-2102PC ultra-violet and visible spectrophotometer of UNICO(Shanghai) Instruments Co., Ltd., epoxy polysiloxane sample the present invention prepared is placed in the quartz colorimetric utensil of 1mm × 1mm × 10mm; Scanning wave band is 200-900nm, and test sample transmittance, its transmittance can reach 90 ~ 95%.
Beneficial effect of the present invention is:
1, because the hydrogen atom In frared spectra on the carbon-carbon double bond of long-chain polysiloxane end group and side base is weak, only have on the Siliciumatom at ortho position and contain methyl electron donating group, therefore the cloud density in double bond is lower, traditional Peracetic Acid, peroxide m-chlorobenzoic acid, the close electrooxidation reagent such as peroxy trifluoroacetic acid is difficult to its epoxidation, and the present invention's epoxidation reagent used is metal complex and 30%H
2o
2the nucleophilic oxygenant of composition, the carbon-carbon double bond more weak to supplied for electronic has good selectivity.
2, the end group on polysiloxane and side base double bond epoxidation are directly prepared epoxy silicone resin by the present invention, avoid the interface compatibility problem that blending and modifying causes, unstable properties; And the shortcoming such as difficult removals of the wayward and catalyzer of modification by copolymerization reaction, this method reaction temperature and, used catalyst is pressed powder and hydrogen peroxide, easily separated and removal, and the preparation for epoxy silicone resin provides a new path.
3, the raw materials octamethylcyclotetrasiloxane of many vinyl polysiloxane can change octaphenylcyclotetrasiloxane into, aminomethyl phenyl cyclotetrasiloxanes etc. are containing the reagent of phenyl, because phenyl has higher specific refractory power and rigidity, light extraction efficiency can be increased using it as LED encapsulation material, make it have good resistance to elevated temperatures and ultra-violet resistance energy, and improve the resistibility of chip to external shock, slow down mechanical vibration, ensure that it normally works.
Accompanying drawing explanation
Fig. 1 is that the liquid epoxy polysiloxane of the embodiment of the present invention 1 is through infrared spectra detection figure.
Embodiment
In the raw material that various embodiments of the present invention are used except the special producer that shows and model, other raw materials are commercially available, and specification is chemical pure.
The model of the various equipment that the present invention is used and the information of manufacturer as follows:
NDJ-1 rotational viscosimeter, Shanghai sharp bearing device Manufacturing Co., Ltd;
UV-2102PC ultra-violet and visible spectrophotometer, UNICO(Shanghai) Instruments Co., Ltd..
Embodiment 1
Thermometer loaded onto by reaction vessel, connect and vacuumize de-watering apparatus, in order with weight parts, add octamethylcyclotetrasiloxane 30 parts, t etram-ethyltetravinylcyclotetrasiloxane 8 parts, vinyl double-seal head 0.4 part, vacuum tightness, below-0.090MPa, opens heating and magnetic stirring apparatus, be warming up to the initial temperature 50 DEG C of setting, dewater 0.5h; Add catalyzer tetramethylammonium hydroxide aqueous solution afterwards, the add-on of Tetramethylammonium hydroxide accounts for 0.03% of mix monomer total mass, change reflux condensing tube, material in bottle is warming up to design temperature 100 DEG C, at a set temperature polyreaction 5h (indicating: now do not need vaccum dewatering device).Reaction terminates rapidly temperature to be raised to more than 140 DEG C decomposition catalysts afterwards, as about pH=7 with pH detection paper tail gas, can continue intensification; Vacuum tightness, below-0.090MPa, is warming up to more than 200 DEG C, de-low-boiling-point substance, and the time is 10-20min, can stop heating, be cooled to the polysiloxane that room temperature can obtain water white ethenyl blocking when observing and flowing out without cut.Yield 87.9%.
Reaction vessel is loaded onto mechanical stirring, thermometer, dropping funnel, with weight parts, add vinyl polysiloxane more than 10 parts, 50 parts of ethyl acetate, 2 parts of tetracarboxylic metal phthalocyanine complex compounds, mechanical stirring is warmed up to 40 DEG C; Drip 10 parts, 30% hydrogen peroxide, dropwise, dropping funnel is taken off, change reflux condensing tube, and react 5h at this temperature; Reaction terminates rear mistake and filters faint yellow solid, and gained clear liquid, with the sodium bisulfite washing of 10%, to the aobvious blueness of starch potassium iodide paper, then washs 2 times with deionized water 50 parts, with anhydrous sodium sulfate drying; Cross and filter siccative, concentrate to obtain colourless liquid epoxy silicone resin, productive rate 52%, transmittance 93%, viscosity 4000mPas.
The epoxy silicone resin of above-mentioned gained is carried out Infrared spectroscopy by infrared chromatograph (Nicolet company 380 of U.S. type), the infrared spectrogram of gained as shown in Figure 1, as can be seen from Figure 1, IR (KBr): 829 (epoxide group), turns out to be containing epoxy group(ing).
Embodiment 2
Thermometer loaded onto by reaction vessel, connect and vacuumize de-watering apparatus, in order with weight parts, add octamethylcyclotetrasiloxane 30 parts, t etram-ethyltetravinylcyclotetrasiloxane 12 parts, vinyl double-seal head 0.6 part, vacuum tightness, below-0.090MPa, opens heating and magnetic stirring apparatus, be warming up to the initial temperature 70 DEG C of setting, dewater 1h; Add catalyzer tetramethylammonium hydroxide aqueous solution afterwards, the add-on of Tetramethylammonium hydroxide accounts for 0.05% of mix monomer total mass, change reflux condensing tube, material in bottle is warming up to design temperature 100 DEG C, at a set temperature polyreaction 5h (indicating: now do not need vaccum dewatering device).Reaction terminates rapidly temperature to be raised to more than 140 DEG C decomposition catalysts afterwards, as about pH=7 with pH detection paper tail gas, can continue intensification; Vacuum tightness, below-0.090MPa, is warming up to more than 200 DEG C, de-low-boiling-point substance, and the time is 10-20min, can stop heating, be cooled to the polysiloxane that room temperature can obtain water white ethenyl blocking when observing and flowing out without cut.Yield 85.2%.
Reaction vessel is loaded onto mechanical stirring, thermometer, dropping funnel, with weight parts, add vinyl polysiloxane more than 10 parts, 50 parts of ethyl acetate, 6 parts of tetracarboxylic metal phthalocyanine complex compounds, mechanical stirring is warmed up to 60 DEG C; Drip 20 parts, 30% hydrogen peroxide, dropwise, dropping funnel is taken off, change reflux condensing tube, and react 5h at this temperature; Reaction terminates rear mistake and filters faint yellow solid, and gained clear liquid, with the sodium bisulfite washing of 10%, to the aobvious blueness of starch potassium iodide paper, then washs 2 times with deionized water 50 parts, with anhydrous sodium sulfate drying; Cross and filter siccative, concentrate to obtain colourless liquid epoxy silicone resin, productive rate 64%, transmittance 93%, viscosity 7000mPas.
Embodiment 3
Thermometer loaded onto by reaction vessel, connect and vacuumize de-watering apparatus, be sequentially added into octamethylcyclotetrasiloxane 30 parts, t etram-ethyltetravinylcyclotetrasiloxane 10 parts, vinyl double-seal head 0.5 part, vacuum tightness is below-0.090MPa, open heating and magnetic stirring apparatus, be warming up to the initial temperature 60 DEG C of setting, dewater 0.5h; Add catalyzer tetramethylammonium hydroxide aqueous solution afterwards, the add-on of Tetramethylammonium hydroxide accounts for 0.04% of mix monomer total mass, change reflux condensing tube, material in bottle is warming up to design temperature 110 DEG C, at a set temperature polyreaction 6h (indicating: now do not need vaccum dewatering device).Reaction terminates rapidly temperature to be raised to more than 140 DEG C decomposition catalysts afterwards, as about pH=7 with pH detection paper tail gas, can continue intensification; Vacuum tightness, below-0.090MPa, is warming up to more than 200 DEG C, de-low-boiling-point substance, and the time is 10-20min, can stop heating, be cooled to the polysiloxane that room temperature can obtain water white ethenyl blocking when observing and flowing out without cut.Yield 86.4%.
Reaction vessel is loaded onto mechanical stirring, thermometer, dropping funnel, add vinyl polysiloxane more than 10 parts, 60 parts of ethyl acetate, 4 parts of tetracarboxylic metal phthalocyanine complex compounds, mechanical stirring is warmed up to 50 DEG C; Drip 40 parts, 30% hydrogen peroxide, dropwise, dropping funnel is taken off, change reflux condensing tube, and react 6h at this temperature; Reaction terminates rear mistake and filters faint yellow solid, and gained clear liquid, with the sodium bisulfite washing of 10%, to the aobvious blueness of starch potassium iodide paper, then washs 2 times with deionized water 50 parts, with anhydrous sodium sulfate drying; Cross and filter siccative, concentrate to obtain colourless liquid epoxy silicone resin, productive rate 56%, transmittance 92%, viscosity 5200mPas.
Claims (9)
1. an epoxy polysiloxane compound, is characterized in that, the transmittance of this compound is between 90 ~ 95%, and the viscosity at room temperature 25 DEG C is between 4000 ~ 7000mPa.s; Its structural formula is as follows:
Wherein, x represents the polymerization degree, and span is 20-30.
2. an epoxidation preparation method for epoxy polysiloxane compound, it is characterized in that, concrete steps are as follows:
(1) preparation of many vinyl polysiloxane
First by octamethylcyclotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane and vinyl double-seal head according to 30:(5-15): at reduced pressure, dewater the mass ratio of (0.2-0.8) 0.5h ~ 1h at 40 DEG C ~ 80 DEG C temperature; Add catalyzer tetramethylammonium hydroxide aqueous solution afterwards, at 90 DEG C ~ 110 DEG C temperature, react 4h ~ 8h, reaction terminates rear decomposition catalyst and removes low-boiling-point substance, obtains many vinyl polysiloxane; Wherein, the add-on of Tetramethylammonium hydroxide accounts for 0.03% ~ 0.05% of mix monomer total mass; The structural formula of many vinyl polysiloxane is as follows:
(2) preparation of epoxy polysiloxane compound
Many vinyl polysiloxane that step (1) prepares are added drop-wise in the solution containing epoxidation reagent, at 30 DEG C ~ 70 DEG C temperature, reaction 3h ~ 6h, purifies and separates obtains epoxy polysiloxane afterwards; Wherein: epoxidation reagent is tetracarboxylic metal phthalocyanine complex compound and 30wt%H
2o
2mixture; Tetracarboxylic metal phthalocyanine complex compound and 30wt%H
2o
2mass ratio be 1:3-1:10; The mass ratio of many vinyl polysiloxane and tetracarboxylic metal phthalocyanine complex compound is 10:2-10:6, and the structural formula of described epoxy polysiloxane is as follows:
3. preparation method according to claim 2, it is characterized in that, in step (1), the mass ratio of octamethylcyclotetrasiloxane and t etram-ethyltetravinylcyclotetrasiloxane, vinyl double-seal head is 30:(8-12): (0.3-0.6).
4. preparation method according to claim 2, is characterized in that, in step (1), dewaters at 50 DEG C ~ 70 DEG C temperature.
5. preparation method according to claim 2, is characterized in that, in step (2), temperature is 40 DEG C ~ 60 DEG C, and the mass ratio of many vinyl polysiloxane and tetracarboxylic metal phthalocyanine complex compound is 10:4.
6. preparation method according to claim 2, is characterized in that, in step (2), described containing in the solution of epoxidation reagent, solvent is ethyl acetate or methyl-sulphoxide.
7. preparation method according to claim 2, is characterized in that, in step (2), described containing in the solution of epoxidation reagent, the mass volume ratio of epoxidation reagent and solvent is 1:4-1:10mg/mL.
8. preparation method according to claim 2, is characterized in that, in step (2), the purifying of epoxy polysiloxane is by first filtering, and the mode of then underpressure distillation realizes.
9. preparation method according to claim 8, is characterized in that, in step (2), the condition of underpressure distillation is: pressure is-0.095MPa, and temperature is 40 DEG C ~ 70 DEG C.
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| CN109400880A (en) * | 2017-08-18 | 2019-03-01 | 北京化工大学 | A kind of the methyl vinyl phenyl silicon rubber and preparation method of high phenyl high-vinyl-content |
| 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 |
| CN111410745A (en) * | 2019-01-07 | 2020-07-14 | 北京化工大学 | Ultra-low temperature-resistant epoxidized silicone rubber and preparation method thereof |
| CN113004524A (en) * | 2019-12-20 | 2021-06-22 | 万华化学集团股份有限公司 | Epoxy-organic silicon resin and preparation method and application thereof |
| CN113004523A (en) * | 2019-12-20 | 2021-06-22 | 万华化学集团股份有限公司 | Epoxy-organic silicon resin and preparation method and application thereof |
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| CN104672459A (en) * | 2015-02-05 | 2015-06-03 | 上海应用技术学院 | Vinyl phenyl silicon resin with side chain containing epoxy group and preparation method of vinyl phenyl silicon resin |
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| CN109400880A (en) * | 2017-08-18 | 2019-03-01 | 北京化工大学 | A kind of the methyl vinyl phenyl silicon rubber and preparation method of high phenyl high-vinyl-content |
| CN109400880B (en) * | 2017-08-18 | 2020-09-04 | 北京化工大学 | Methyl vinyl phenyl silicone rubber with high phenyl content and high vinyl content and preparation method thereof |
| CN111410745A (en) * | 2019-01-07 | 2020-07-14 | 北京化工大学 | Ultra-low temperature-resistant epoxidized silicone rubber and preparation method thereof |
| CN113004524A (en) * | 2019-12-20 | 2021-06-22 | 万华化学集团股份有限公司 | Epoxy-organic silicon resin and preparation method and application thereof |
| CN113004523A (en) * | 2019-12-20 | 2021-06-22 | 万华化学集团股份有限公司 | Epoxy-organic silicon resin and preparation method and application thereof |
| CN113004523B (en) * | 2019-12-20 | 2022-08-05 | 万华化学集团股份有限公司 | Epoxy-organic silicon resin and preparation method and application 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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Effective date of registration: 20180706 Address after: No. 3288, Shanghai City, Jia Zhu highway Patentee after: SHANGHAI RESIN FACTORY Co.,Ltd. Address before: 200235 Caobao Road, Xuhui District, Shanghai, No. 120-121 Patentee before: Shanghai Institute of Technology |