CN103030812A - Modified phenyl silsesquioxane and preparation method thereof - Google Patents

Modified phenyl silsesquioxane and preparation method thereof Download PDF

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CN103030812A
CN103030812A CN2013100051140A CN201310005114A CN103030812A CN 103030812 A CN103030812 A CN 103030812A CN 2013100051140 A CN2013100051140 A CN 2013100051140A CN 201310005114 A CN201310005114 A CN 201310005114A CN 103030812 A CN103030812 A CN 103030812A
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modification
phenyl silsesquioxane
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牟秋红
刘月涛
彭丹
李金辉
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Shandong Shanke Ruisen New Material Technology Co ltd
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New Material Institute of Shandong Academy of Sciences
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Abstract

The invention relates to modified phenyl silsesquioxane and a preparation method thereof. The molecular formula of the modified phenyl silsesquioxane is (R(R')2SiO0.5)a (Me2SiO)b (MePhSiO)c (PhSiO1.5)d, wherein R is Me, H or unsaturated alkene with the tail end being carbon-carbon double bond and the carbon atom number being 2-10; R' is Me, Ph or long chain saturated alkane with the carbon atom number being 1-10; the numerical values of a, b and c are same or different and are within 0.1-0.6; and the numerical value of d is 0.2-0.9, and the sum of a, b, c and d is 1. Polymethyl phenyl siloxane blocked by hydroxyl and phenyl silane are used as raw materials to be prepared into the modified phenyl silsesquioxane through processes of hydrolysis, polycondensation and the like. The modified phenyl silsesquioxane has the advantages of high light transmittance, good insulativity, radiation resistance, high and low temperature resistance and the like. The reaction system of the preparation method is homogeneous, the reaction condition is mild and is easily controlled, the product yield is high, the method is suitable for industrialized production, and the post-processing is complete.

Description

A kind of modification phenyl silsesquioxane and preparation method thereof
Technical field
The present invention relates to a kind of modification phenyl silsesquioxane and preparation method thereof, belong to the organosilicon macromolecule technical field.
Background technology
Polyphenylsilsesquioxane (PPSQ) is the polymkeric substance that contains phenyl silsesquioxane structure, and structural formula is (PhSiO 1.5) nBecause of its special microtexture, have the performances such as excellent heat-resisting, heat-resisting oxidation, weather-proof, chemically-resistant, be dissolvable in water the organic solvents such as benzene, tetrahydrofuran (THF), methylene dichloride, and can curtain coating become water white transparency, tough and tensile film, have excellent optical transparence and dielectric properties after the curing, at optoelectronic areas such as white-light LED encapsulations huge application prospect is arranged.
Pass through PhSiX 3(X=Cl, OMe, OEt, OAc etc.) hydrolytic condensation is the modal mode of preparation PPSQ, but by PhSiX 3Formed PPSQ is hard and crisp in homopolymerization, with PhSiCl 3With MeSiCl 2, MePhSiCl 2, Ph 2SiCl 2Carry out cohydrolysis reaction, often obtain the hydrolysate of nonspecific regular clean structure, can not give full play to the silsesquioxane structural advantage.To enlarge to a great extent its Application Areas if can improve the toughness of PPSQ.
In order to improve silsesquioxane toughness, researcher has adopted the whole bag of tricks to attempt.The people such as Hu Chunye (elastomerics, 1996,3(6): 14-19; Elastomerics, 1997,7(2): 38-42) hydroxy silicon oil is dissolved in toluene and also adds successively 45 ℃ of lower reaction 24h such as phenyltrimethoxysila,e, methyl alcohol, ammoniacal liquor, obtain white polydimethyl-phenyl silsesquioxane multipolymer behind desolventizing and the small molecules, add under dibutyl tin dilaurate, the aminopropyl triethoxysilane room temperature and vulcanize, can obtain the elastomerics of good mechanical performance.The people such as He Yifei (New Chemical Materials, 2006,34(5): 38-42) conduct in-depth research on this basis, develop polydimethylsiloxane with good curability-trapezoidal silicone copolymers film of phenyl sesquialter, film surface is smooth, has good molecule screening crown_interception.But the modification of above research hydroxy silicon oil and with the reaction of resin in all need to add metal ion and can affect its dielectric properties, electrical insulating property is descended.
Patent CN101544763A has reported silicone oil and polysilsesquioxane has been dissolved in the solvent, keep solid content 50～80%, in being 0～3 sour environment, 80% humidity, PH place for some time, cast or coating film forming after taking out, obtain the modification silsesquioxane material of transparent insulation, toughness and excellent strength, but material cured is inhomogeneous, and has small molecules to discharge in the solidification process, and the dimensional stabilizing of material is bad.
Summary of the invention
The object of the present invention is to provide a kind of modification phenyl silsesquioxane and preparation method thereof, what prepare is material modified, and this modification phenyl silsesquioxane has the advantages such as transmittance height, good insulating, radiation hardness, high-low temperature resistant.
The present invention is achieved by the following technical programs:
A kind of modification phenyl silsesquioxane, its molecular formula is:
（R（R’） 2SiO 0.5） a（Me 2SiO） b（MePhSiO） c（PhSiO 1.5） d；
Wherein, R is that Me, H or end are that the unsaturated olefin of carbonatoms between 2～10 of carbon-carbon double bond, R ' are the long-chain saturated alkane base between Me, Ph or the carbonatoms 1～10, and the numerical value of a, b, c is identical or different all between 0.1～0.6; The numerical value of d is between 0.2～0.9, and a+b+c+d=1.
Described modification phenyl silsesquioxane, its structural formula is preferably:
Figure BDA00002710751700021
The numerical value of a, b is between 0.1～0.4; The numerical value of c is between 0.3～0.6, and a+b+c=1; Vi represents vinyl.
The preparation method of above-mentioned modification phenyl silsesquioxane comprises that step is as follows:
(1) end-capping reagent, an acidic catalyst, water, non-polar solvent are mixed into mixed solution, with phenyl silane with slowly be added dropwise to aforementioned mixed solution after isopyknic non-polar solvent evenly mixes, the 0-20 ℃ of reaction that is hydrolyzed, after dropwising, normal-temperature reaction 1h, be warming up to afterwards 60-70 ℃ of solvent and begin to reflux, and back flow reaction 5-6h; Take out organic layer after reaction finishes, be washed to neutrality, obtain hydrolyzation material;
(2) in the reactor of hydrolyzation material adding with water trap with aminomethyl phenyl hydroxy silicon oil, basic catalyst, step (1), be warming up to gradually the solvent refluxing in the hydrolyzation material, then remove the part organic solvent, make solid content maintenance 50-75% in the reactor, keep afterwards back flow reaction 5-6h, after reaction finishes, the acid neutralization basic catalyst, filter, decompression desolventizes, and can obtain target product.
In above-mentioned steps (1) system in step (1) system concentration of an acidic catalyst in water be 3-10mol/L; The mol ratio of water and phenyl silane is 3-10:1; End-capping reagent and phenyl silane mol ratio are 1-8:4; Non-polar solvent cumulative volume and phenyl silane volume ratio 1.5-4:1.
The described end-capping reagent of step (1) is 1,1,3,3-tetramethyl--1,3-divinyl disiloxane, hexamethyldisiloxane, decamethyl tetrasiloxane, 1,3-dimethyl-1,1,3, one or more in 3-tetraphenyl-sily oxide.
The described non-polar solvent of step (1) all is selected from toluene, benzene, dimethylbenzene, gasoline, solvent oil, ether, sherwood oil, normal hexane.
The described an acidic catalyst of step (1) is one or more in hydrochloric acid, sulfuric acid, the trifluoromethanesulfonic acid.
The described phenyl silane of step (1) is in phenyl-trichloro-silicane, phenyltrimethoxysila,e, the phenyl triethoxysilane one or more.Content 〉=99.95% if can not reach, can adopt the method for rectifying further to remove impurity.
The mass ratio of the hydrolyzation material of aminomethyl phenyl hydroxy silicon oil and step (1) is 1:2-15 in the step (2), and the basic catalyst consumption is aminomethyl phenyl hydroxy silicon oil and hydrolyzation material total mass 0.001-0.01%.
The described aminomethyl phenyl hydroxy silicon oil of step (2), its structural formula is:
Figure BDA00002710751700031
Wherein, m, n are the polymerization degree, m=1-30, n=1-20.
The described basic catalyst of step (2) is one or more among KOH, NaOH or the LiOH.
The present invention is to be raw material by hydroxy-end capped PSI and phenyl silane, prepares through techniques such as hydrolysis, polycondensations.The method reaction system is homogeneous phase, and reaction conditions is gentle, and is easy to control, and product yield is high, is suitable for industrialization production, and aftertreatment is complete.Multipolymer can adopt silicon hydrogen addition vulcanization mode to be cured reaction, and completion of cure discharges the product size good stability without small molecules in the solidification process.The material modified excellent product performance for preparing, steady quality, reliable, and this modification phenyl silsesquioxane has the advantages such as transmittance height, good insulating, radiation hardness, high-low temperature resistant.
Description of drawings
Fig. 1 is the infrared spectrogram of product of the present invention.
Embodiment
Below by embodiment, technical scheme of the present invention is done further specific description.
Use the UV1750 spectrophotometer of Japanese Shimadzu company to test the transmittance of modification silsesquioxane material in the 300-800nm wavelength region, thickness of sample 4mm; Use LX-D, the LX-A type Shore durometer test material hardness of Yueqing City Hypon Instr Ltd. according to standard GB/T/T531-1999; Use Shenzhen ten thousand tests to test the ETM104C type universal tensile testing machine test material tensile strength of equipment company limited according to standard GB/T/T528-1998.
Embodiment 1:
In the 1000ml there-necked flask of stirring, thermometer and dropping funnel is housed, add 200ml toluene, hydrochloric acid 15g37%(v/v), the 59g deionized water, 37.5g tetramethyl divinyl disiloxane splashes into the mixture (time for adding is 2h) of 200ml phenyltrimethoxysila,e and 200ml toluene.Hydrolysis temperature is 5-10 ℃, after dropwising, continues reaction 2h under the normal temperature.Then progressively be warming up to 70 ℃ of refluxing toluene 5h.Stopped reaction leaves standstill and tells sour water, and oil reservoir washes with water to neutrality, and drying obtains hydrolyzate, and yield is more than 93%.The PSI that 60g is hydroxy-end capped and the hydrolysis material that obtains place 500ml that the reaction flask of water trap is housed, add 0.4g potassium hydroxide, mix, be warming up to solvent refluxing, utilize water trap to emit water and partial solvent that polycondensation generates, keep in the reaction flask solid content about 70%, continue polycondensation 5h.Reaction adds in the acetic acid and basic catalyst after finishing, and filters, and decompression desolventizes, and can obtain target product, specific refractory power 1.54, and productive rate is 87%.After hydrogeneous basic phenyl polysiloxane curing, resulting materials transmittance 89%(4mm), hardness 60A, tensile strength 2.8MPa.
Embodiment 2:
Use the hydrolysis reaction catalyzer hydrochloric acid of embodiment 1 instead the 2g trifluoromethanesulfonic acid, the PSI reaction that hydrolysis material and 75g are hydroxy-end capped, potassium hydroxide consumption 0.46g, all the other steps are identical with embodiment 1.The target product productive rate is 90%.After hydrogeneous basic phenyl polysiloxane curing, resulting materials transmittance 90%(4mm), hardness 40A, tensile strength 2.2MPa.
Embodiment 3:
Use the hydrolysis reaction catalyzer hydrochloric acid of embodiment 1 instead 1g trifluoromethanesulfonic acid and 7.5g37%(v/v) hydrochloric acid, the hydroxy-end capped PSI of hydrolysis material and 40g reacts, all the other steps are identical with embodiment 1.The target product productive rate is 90%.After hydrogeneous basic phenyl polysiloxane curing, resulting materials transmittance 90%(4mm), hardness 30D, tensile strength 3.5MPa.
Embodiment 4:
To be hydrolyzed the hydroxy-end capped PSI reaction of material and 30g, all the other steps are identical with embodiment 2.The target product productive rate is 90%.After hydrogeneous basic phenyl polysiloxane curing, resulting materials transmittance 91%(4mm), hardness 50D, tensile strength 4.1MPa.
Fig. 1 is the infrared spectrogram of present embodiment PSI-phenyl silsesquioxane multipolymer.As can be seen from Figure 1,1632cm -1, the absorption peak at 1428 places is the absorption peak of silicon phenyl, 1250cm -1The absorption peak at place is the absorption peak of silicon methyl, 3200～3700cm -1With 830～950cm -1The absorption peak that does not occur the SiOH group in the zone, this explanation polycondensation is than more completely.The target product of polycondensation can be from 1000～1100cm -1The charateristic avsorption band of Si-O-Si reflect.
Only be specific embodiments of the invention for example more than, the present invention is not limited to above-described embodiment, and many operative combination can also be arranged.The all scenario that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.

Claims (10)

1. modification phenyl silsesquioxane, its molecular formula is:
（R（R'） 2SiO 0.5） a（Me 2SiO） b（MePhSiO） c（PhSiO 1.5） d；
Wherein, R is that Me, H or end are that the unsaturated olefin of carbonatoms between 2～10 of carbon-carbon double bond, R ' are the long-chain saturated alkane base between Me, Ph or the carbonatoms 1～10, and the numerical value of a, b, c is identical or different all between 0.1～0.6; The numerical value of d is between 0.2～0.9, and a+b+c+d=1.
2. a kind of modification phenyl silsesquioxane according to claim 1 is characterized in that its structural formula is:
Figure FDA00002710751600011
The numerical value of a, b is between 0.1～0.4; The numerical value of c is between 0.3～0.6, and a+b+c=1; Vi represents vinyl.
3. the preparation method of claim 1 or 2 described modification phenyl silsesquioxanes is characterized in that, comprises that step is as follows:
(1) end-capping reagent, an acidic catalyst, water, non-polar solvent are mixed into mixed solution, with phenyl silane with slowly be added dropwise to aforementioned mixed solution after isopyknic non-polar solvent evenly mixes, the 0-20 ℃ of reaction that is hydrolyzed, after dropwising, normal-temperature reaction 1h, be warming up to afterwards 60-70 ℃ of solvent and begin to reflux, and back flow reaction 5-6h; Take out organic layer after reaction finishes, be washed to neutrality, obtain hydrolyzation material;
(2) in the reactor of hydrolyzation material adding with water trap with aminomethyl phenyl hydroxy silicon oil, basic catalyst, step (1), be warming up to gradually the solvent refluxing in the hydrolyzation material, then remove the part organic solvent, make solid content maintenance 50-75% in the reactor, keep afterwards back flow reaction 5-6h, after reaction finishes, the acid neutralization basic catalyst, filter, decompression desolventizes, and can obtain target product.
4. the preparation method of modification phenyl silsesquioxane according to claim 3 is characterized in that, the concentration of an acidic catalyst in water is 3-10mol/L in step (1) system; The mol ratio of water and phenyl silane is 3-10:1; End-capping reagent and phenyl silane mol ratio are 1-8:4; Non-polar solvent cumulative volume and phenyl silane volume ratio 1.5-4:1.
5. the preparation method of modification phenyl silsesquioxane according to claim 3, it is characterized in that, the described end-capping reagent of step (1) is 1,1,3,3-tetramethyl--1,3-divinyl disiloxane, hexamethyldisiloxane, decamethyl tetrasiloxane, 1,3-dimethyl-1,1, in 3,3-tetraphenyl-sily oxide one or more.
6. the preparation method of modification phenyl silsesquioxane according to claim 3 is characterized in that, the described an acidic catalyst of step (1) is one or more in hydrochloric acid, sulfuric acid, the trifluoromethanesulfonic acid.
7. the preparation method of modification phenyl silsesquioxane according to claim 3 is characterized in that, the described phenyl silane of step (1) is in phenyl-trichloro-silicane, phenyltrimethoxysila,e, the phenyl triethoxysilane one or more.
8. the preparation method of modification phenyl silsesquioxane according to claim 3, it is characterized in that, the mass ratio of the hydrolyzation material of aminomethyl phenyl hydroxy silicon oil and step (1) is 1:2-15 in the step (2), and the basic catalyst consumption is aminomethyl phenyl hydroxy silicon oil and hydrolyzation material total mass 0.001-0.01%.
9. the preparation method of modification phenyl silsesquioxane according to claim 3 is characterized in that, the described aminomethyl phenyl hydroxy silicon oil of step (2), and its structural formula is:
Figure FDA00002710751600021
Wherein, m, n are the polymerization degree, m=1-30, n=1-20.
10. the preparation method of modification phenyl silsesquioxane according to claim 3 is characterized in that, the described basic catalyst of step (2) is one or more among KOH, NaOH or the LiOH.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104211965A (en) * 2013-06-03 2014-12-17 北京化工大学 Preparation method for net-like methyl phenyl vinyl polysiloxane for LED packaging
CN109735203A (en) * 2018-12-25 2019-05-10 陕西科技大学 A kind of semiclosed caged trifunctional epoxy ether POSS combination material, coating and preparation method
CN110483783A (en) * 2019-08-16 2019-11-22 湖北兴瑞硅材料有限公司 A kind of phenyl vinyl polysiloxane preparation method

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KR100601913B1 (en) * 2003-03-11 2006-07-14 주식회사 엘지화학 Organic silicate film for bright-enhanced organic light emitting diode
JP2008280420A (en) * 2007-05-09 2008-11-20 Chisso Corp Crosslinkable siloxane polymer, siloxane-based crosslinkable composition and silicone membrane
CN101431139A (en) * 2007-11-08 2009-05-13 菲利浦斯光学有限公司 Silicone resin for protecting a light transmitting surface of an optoelectronic device
CN101544763A (en) * 2008-03-24 2009-09-30 中国科学院化学研究所 Modified silicone resin and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1759147A (en) * 2002-12-13 2006-04-12 博士伦公司 High refractive index polysiloxane prepolymers
KR100601913B1 (en) * 2003-03-11 2006-07-14 주식회사 엘지화학 Organic silicate film for bright-enhanced organic light emitting diode
JP2008280420A (en) * 2007-05-09 2008-11-20 Chisso Corp Crosslinkable siloxane polymer, siloxane-based crosslinkable composition and silicone membrane
CN101431139A (en) * 2007-11-08 2009-05-13 菲利浦斯光学有限公司 Silicone resin for protecting a light transmitting surface of an optoelectronic device
CN101544763A (en) * 2008-03-24 2009-09-30 中国科学院化学研究所 Modified silicone resin and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104211965A (en) * 2013-06-03 2014-12-17 北京化工大学 Preparation method for net-like methyl phenyl vinyl polysiloxane for LED packaging
CN109735203A (en) * 2018-12-25 2019-05-10 陕西科技大学 A kind of semiclosed caged trifunctional epoxy ether POSS combination material, coating and preparation method
CN109735203B (en) * 2018-12-25 2021-01-29 陕西科技大学 Semi-closed cage-shaped trifunctional epoxy ether group POSS (polyhedral oligomeric silsesquioxane) composite material, paint and preparation method
CN110483783A (en) * 2019-08-16 2019-11-22 湖北兴瑞硅材料有限公司 A kind of phenyl vinyl polysiloxane preparation method
CN110483783B (en) * 2019-08-16 2021-08-31 湖北兴瑞硅材料有限公司 Preparation method of phenyl vinyl silicone resin

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