CN103030812B - Modified phenyl silsesquioxane and preparation method thereof - Google Patents
Modified phenyl silsesquioxane and preparation method thereof Download PDFInfo
- Publication number
- CN103030812B CN103030812B CN201310005114.0A CN201310005114A CN103030812B CN 103030812 B CN103030812 B CN 103030812B CN 201310005114 A CN201310005114 A CN 201310005114A CN 103030812 B CN103030812 B CN 103030812B
- Authority
- CN
- China
- Prior art keywords
- phenyl
- preparation
- modification
- phenyl silsesquioxane
- reaction
- 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
Landscapes
- Silicon Polymers (AREA)
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
Technical field
The present invention relates to a kind of modification phenyl silsesquioxane and preparation method thereof, belong to organosilicon macromolecule technical field.
Background technology
Polyphenylsilsesquioxane (PPSQ) is the polymkeric substance containing phenyl silsesquioxane structure, and structural formula is (PhSiO
1.5)
n.Because of the microtexture that it is special, there is the performances such as excellent heat-resisting, resistance to thermooxidizing, weather-proof, chemically-resistant, be dissolvable in water the organic solvents such as benzene, tetrahydrofuran (THF), methylene dichloride, and curtain coating can become water white transparency, tough and tensile film, there are after solidification excellent optical transparence and dielectric properties, have huge application prospect at optoelectronic areas such as white-light LED encapsulations.
Pass through PhSiX
3(X=Cl, OMe, OEt, OAc etc.) hydrolytic condensation is the modal mode of preparation PPSQ, but by PhSiX
3the PPSQ that homopolymerization is formed is hard and crisp, by PhSiCl
3with MeSiCl
2, MePhSiCl
2, Ph
2siCl
2carry out cohydrolysis reaction, often obtain the hydrolysate of nonspecific regular clean structure, silsesquioxane structural advantage can not be given full play to.If the toughness can improving PPSQ will expand its Application Areas to a great extent.
In order to improve silsesquioxane toughness, researcher have employed various method and attempts.The people such as Hu Chunye (elastomerics, 1996,3(6): 14-19; Elastomerics, 1997,7(2): 38-42) hydroxy silicon oil is dissolved at toluene also adds phenyltrimethoxysila,e, methyl alcohol, ammoniacal liquor etc. 45 DEG C successively and reacts 24h, except obtaining white polydimethyl-phenyl silsesquioxane multipolymer after desolventizing and small molecules, carry out sulfuration under adding dibutyl tin dilaurate, aminopropyl triethoxysilane room temperature, the elastomerics of good mechanical performance can be obtained.The people such as He Yifei (New Chemical Materials, 2006,34(5): 38-42) conduct in-depth research on this basis, develop the polydimethylsiloxane-phenyl sesquialter ladder siloxane copolymer film with good curability, film surface is smooth, has good molecule screening crown_interception.But more than study hydroxy silicon oil modification and with the reaction of resin in all need to add metal ion and can affect its dielectric properties, electrical insulating property is declined.
Patent CN101544763A reports and is dissolved in solvent by silicone oil and polysilsesquioxane, keep solid content 50 ~ 80%, for some time is placed in the sour environment of 0 ~ 3 at 80% humidity, PH, cast or coating film forming after taking out, obtain the modification silsesquioxane materials of transparent insulation, toughness and excellent strength, but material cured is uneven, and have small molecules to discharge in solidification process, 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 advantages such as transmittance is high, 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, the unsaturated olefin of carbonatoms between 2 ~ 10 of R to be Me, H or end be carbon-carbon double bond, R ' is the long-chain saturated alkane base between Me, Ph or 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:
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 step as follows:
(1) end-capping reagent, an acidic catalyst, water, non-polar solvent are mixed into mixed solution, aforementioned mixed solution is slowly added dropwise to by after phenyl silane and isopyknic non-polar solvent Homogeneous phase mixing, the 0-20 DEG C of reaction that is hydrolyzed, after dropwising, normal-temperature reaction 1h, be warming up to 60-70 DEG C of solvent afterwards and start backflow, and back flow reaction 5-6h; Reaction terminates rear taking-up organic layer, is washed to neutrality, obtains hydrolyzation material;
(2) hydrolyzation material of aminomethyl phenyl hydroxy silicon oil, basic catalyst, step (1) is added in the reactor with water trap, be warming up to the solvent refluxing in hydrolyzation material gradually, then part organic solvent is removed, make solid content in reactor keep 50-75%, keep back flow reaction 5-6h afterwards, after reaction terminates, acid neutralization basic catalyst, filter, decompression desolventizes, and can obtain target product.
In above-mentioned steps (1) system, in step (1) system, the concentration of an acidic catalyst in water is 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.
End-capping reagent described in step (1) is one or more in 1,1,3,3-tetramethyl--1,3-divinyl disiloxane, hexamethyldisiloxane, decamethyl tetrasiloxane, 1,3-dimethyl-1,1,3,3-tetraphenyl-sily oxide.
Non-polar solvent described in step (1) is all selected from toluene, benzene, dimethylbenzene, gasoline, solvent oil, ether, sherwood oil, normal hexane.
An acidic catalyst described in step (1) is one or more in hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid.
Phenyl silane described in step (1) is one or more in phenyl-trichloro-silicane, phenyltrimethoxysila,e, phenyl triethoxysilane.Content >=99.95%, if can not reach, can adopt the method for rectifying to remove impurity further.
In step (2), the mass ratio of the hydrolyzation material of aminomethyl phenyl hydroxy silicon oil and step (1) is 1:2-15, and basic catalyst consumption is aminomethyl phenyl hydroxy silicon oil and hydrolyzation material total mass 0.001-0.01%.
Aminomethyl phenyl hydroxy silicon oil described in step (2), its structural formula is:
wherein, m, n are the polymerization degree, m=1-30, n=1-20.
Basic catalyst described in step (2) is one or more in KOH, NaOH or LiOH.
The present invention is 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 easy to control, product yield is high, and be suitable for industrialization and produce, aftertreatment is complete.Multipolymer can adopt Si―H addition reaction vulcanization to be cured reaction, completion of cure, without small molecules release in solidification process, and product size good stability.The material modified excellent product performance prepared, steady quality, reliable, and this modification phenyl silsesquioxane has advantages such as transmittance is high, good insulating, radiation hardness, high-low temperature resistant.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of product of the present invention.
Embodiment
Below by embodiment, technical scheme of the present invention is done more specifically bright.
The UV1750 spectrophotometer of Japanese Shimadzu Corporation is used to test the transmittance of modification silsesquioxane materials in 300-800nm wavelength region, thickness of sample 4mm; LX-D, LX-A type Shore durometer test material hardness of Yueqing City Hypon Instrument Ltd. is used according to standard GB/T/T531-1999; Shenzhen ten thousand is used to survey the ETM104C type universal tensile testing machine test material tensile strength of testing installation company limited according to standard GB/T/T528-1998.
Embodiment 1:
In the 1000ml there-necked flask that stirring, thermometer and dropping funnel are housed, add 200ml toluene, hydrochloric acid 15g37%(v/v), 59g deionized water, 37.5g tetramethyl divinyl disiloxane, the mixture (time for adding is 2h) of instillation 200ml phenyltrimethoxysila,e and 200ml toluene.Hydrolysis temperature is 5-10 DEG C, after dropwising, continues reaction 2h under normal temperature.Then 70 DEG C of refluxing toluene 5h are progressively warming up to.Stopped reaction, leave standstill and separate sour water, oil reservoir washes with water to neutrality, and dry, obtain hydrolyzate, yield is more than 93%.PSI hydroxy-end capped for 60g and the hydrolysis material obtained are placed in the reaction flask that 500ml is equipped with water trap, add 0.4g potassium hydroxide, mix, be warming up to solvent refluxing, water trap is utilized to release water and the partial solvent of polycondensation generation, keep solid content about 70% in reaction flask, continue polycondensation 5h.After reaction terminates, add in acetic acid and basic catalyst, filter, decompression desolventizes, and can obtain target product, specific refractory power 1.54, and productive rate is 87%.After solidifying with hydrogeneous base phenyl polysiloxane, resulting materials transmittance 89%(4mm), hardness 60A, tensile strength 2.8MPa.
Embodiment 2:
Use the hydrolysis reaction hydrochloric of embodiment 1 instead 2g trifluoromethanesulfonic acid, hydrolysis material and the hydroxy-end capped PSI of 75g react, and potassium hydroxide consumption 0.46g, all the other steps are identical with embodiment 1.Target product productive rate is 90%.After solidifying with hydrogeneous base phenyl polysiloxane, resulting materials transmittance 90%(4mm), hardness 40A, tensile strength 2.2MPa.
Embodiment 3:
Use the hydrolysis reaction hydrochloric of embodiment 1 instead 1g trifluoromethanesulfonic acid and 7.5g37%(v/v) hydrochloric acid, hydrolysis material and the hydroxy-end capped PSI of 40g react, and all the other steps are identical with embodiment 1.Target product productive rate is 90%.After solidifying with hydrogeneous base phenyl polysiloxane, resulting materials transmittance 90%(4mm), hardness 30D, tensile strength 3.5MPa.
Embodiment 4:
Hydrolysis material and the hydroxy-end capped PSI of 30g are reacted, all the other steps are identical with embodiment 2.Target product productive rate is 90%.After solidifying with hydrogeneous base phenyl polysiloxane, resulting materials transmittance 91%(4mm), hardness 50D, tensile strength 4.1MPa.
Fig. 1 is the infrared spectrogram of the 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
-1do not occur the absorption peak of SiOH group in region, this illustrates that polycondensation is than more completely.The target product of polycondensation can from 1000 ~ 1100cm
-1the charateristic avsorption band of Si-O-Si reflect.
More than illustrating is only specific embodiments of the invention, and the present invention is not limited to above-described embodiment, can also have many operative combination.The all scenario that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, is all considered to be protection scope of the present invention.
Claims (10)
1. a modification phenyl silsesquioxane, its molecular formula is:
(R(R’)
2SiO
0.5)
a(Me
2SiO)
b(MePhSiO)
c(PhSiO
1.5)
d；
Wherein, the unsaturated olefin of carbonatoms between 2 ~ 10 of R to be Me, H or end be carbon-carbon double bond, R ' is the saturated alkane base between Me, Ph or 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, it is characterized in that, its structural formula is:
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 modification phenyl silsesquioxane described in claim 1 or 2, is characterized in that, comprise step as follows:
(1) end-capping reagent, an acidic catalyst, water, non-polar solvent are mixed into mixed solution, aforementioned mixed solution is slowly added dropwise to by after phenyl silane and isopyknic non-polar solvent Homogeneous phase mixing, the 0-20 DEG C of reaction that is hydrolyzed, after dropwising, normal-temperature reaction 1h, be warming up to 60-70 DEG C of solvent afterwards and start backflow, and back flow reaction 5-6h; Reaction terminates rear taking-up organic layer, is washed to neutrality, obtains hydrolyzation material;
(2) hydrolyzation material of aminomethyl phenyl hydroxy silicon oil, basic catalyst, step (1) is added in the reactor with water trap, be warming up to the solvent refluxing in hydrolyzation material gradually, then part organic solvent is removed, make solid content in reactor keep 50-75%, keep back flow reaction 5-6h afterwards, after reaction terminates, 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, in step (1) system, the concentration of an acidic catalyst in water is 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.
5. the preparation method of modification phenyl silsesquioxane according to claim 3, it is characterized in that, end-capping reagent described in step (1) is 1,1,3,3-tetramethyl--1,3-divinyl disiloxane, hexamethyldisiloxane, decamethyl tetrasiloxane, 1,3-dimethyl-1,1, one or more in 3,3-tetraphenyl-sily oxide.
6. the preparation method of modification phenyl silsesquioxane according to claim 3, is characterized in that, an acidic catalyst described in step (1) is one or more in hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid.
7. the preparation method of modification phenyl silsesquioxane according to claim 3, is characterized in that, the phenyl silane described in step (1), is one or more in phenyl-trichloro-silicane, phenyltrimethoxysila,e, phenyl triethoxysilane.
8. the preparation method of modification phenyl silsesquioxane according to claim 3, it is characterized in that, in step (2), the mass ratio of the hydrolyzation material of aminomethyl phenyl hydroxy silicon oil and step (1) is 1:2-15, and 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 aminomethyl phenyl hydroxy silicon oil described in step (2), and its structural formula is:
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 basic catalyst described in step (2) is one or more in KOH, NaOH or LiOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310005114.0A CN103030812B (en) | 2013-01-07 | 2013-01-07 | Modified phenyl silsesquioxane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310005114.0A CN103030812B (en) | 2013-01-07 | 2013-01-07 | Modified phenyl silsesquioxane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103030812A CN103030812A (en) | 2013-04-10 |
| CN103030812B true CN103030812B (en) | 2015-03-04 |
Family
ID=48018242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310005114.0A Active CN103030812B (en) | 2013-01-07 | 2013-01-07 | Modified phenyl silsesquioxane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103030812B (en) |
Families Citing this family (3)
| 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 |
| 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 |
| 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 |
Citations (5)
| 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 |
-
2013
- 2013-01-07 CN CN201310005114.0A patent/CN103030812B/en active Active
Patent Citations (5)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103030812A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103059306B (en) | High-refractive index transparent silicone resin and preparation method thereof | |
| CN103012798B (en) | Preparation method of methyl phenyl vinyl silicone resin | |
| CN102408565B (en) | Preparation method for phenyl hydrogen-containing silicone oil | |
| CN102643304B (en) | A kind of preparation method of cage modle phenyl sesquisiloxane | |
| CN104045831B (en) | A kind of siloxanes abutting ladder poly-siloxane and preparation method thereof | |
| CN106750312B (en) | Phenyl DT (bismuth telluride) silicone resin and preparation method thereof | |
| WO2009119253A1 (en) | Silanol-group-containing curable cage-type silsesquioxane compound, cage-structure-containing curable silicone copolymer, processes for producing these, and curable resin composition | |
| CN105254661A (en) | Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof | |
| CN105802532A (en) | Silicon boron tackifier, preparation method thereof and application thereof in double-component LED packaging gel | |
| CN104910384B (en) | A kind of preparation method of acetylenic glycols b-oxide modified polyorganosiloxane | |
| KR20110132533A (en) | Composition for thermosetting silicone resin | |
| WO2016082287A1 (en) | Mdq phenyl vinyl silicone resin and preparation method therefor | |
| CN104829841B (en) | A kind of organosilicon macromolecule material and preparation method thereof | |
| CN103030812B (en) | Modified phenyl silsesquioxane and preparation method thereof | |
| CN102898650A (en) | T-chain unit phenyl-containing MTQ silicon resin and preparation method thereof | |
| CN108329477A (en) | A kind of organic silicon rigidity-increasing stick and preparation method thereof | |
| CN110452386B (en) | Preparation and application of polyfunctional group POSS type organic silicon curing agent | |
| CN102796264B (en) | Macromolecular organic silicon modifier as well as preparation method and application thereof in surface treatment of hydroxide flame retardant | |
| CN104086587A (en) | Preparation method for cage-type dec(glycidyl silsesquioxane) | |
| CN110229339A (en) | A kind of phenylethylene based siloxane resins, high refractive index LED encapsulation silicon resin composition and preparation method thereof | |
| CN109705352A (en) | A kind of vinyl polysiloxane and its preparation method and application | |
| TW201809146A (en) | Formulation containing a metal aprotic organosilanoxide compound | |
| JP2014047207A (en) | Novel organic silicon compound and its manufacturing method | |
| CN100497407C (en) | Aryne resin containing silicone | |
| CN103012456A (en) | Method for preparing organic silicon oligomer for encapsulating large-power light emitting diode (LED) |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230322 Address after: 250117 Block F, Qilu Gate, Greenland, Huaiyin District, Jinan City, Shandong Province 2605-U Patentee after: Shandong Shanke Ruisen New Material Technology Co.,Ltd. Address before: 250014 No. 19, ASTRI Road, Lixia District, Shandong, Ji'nan Patentee before: NEW MATERIAL INSTITUTE OF SHANDONG ACADEMY OF SCIENCES |