CN110483777B - Synthesis method of poly-silicon hydroxyl POSS - Google Patents

Synthesis method of poly-silicon hydroxyl POSS Download PDF

Info

Publication number
CN110483777B
CN110483777B CN201910854383.1A CN201910854383A CN110483777B CN 110483777 B CN110483777 B CN 110483777B CN 201910854383 A CN201910854383 A CN 201910854383A CN 110483777 B CN110483777 B CN 110483777B
Authority
CN
China
Prior art keywords
poss
hydroxyl poss
polysilsesquioxane
catalyst
poly
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
Application number
CN201910854383.1A
Other languages
Chinese (zh)
Other versions
CN110483777A (en
Inventor
刘丽
许耀元
黄玉东
钟正祥
龙军
张润泽
王昱璎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201910854383.1A priority Critical patent/CN110483777B/en
Publication of CN110483777A publication Critical patent/CN110483777A/en
Application granted granted Critical
Publication of CN110483777B publication Critical patent/CN110483777B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

A method for synthesizing polysilsesquioxane POSS, which belongs to the technical field of POSS preparation. The method comprises the following steps: the method comprises the following steps: mixing the methanol solution and tetrapropoxysilane; step two: adding tetramethylammonium hydroxide/ethylammonium hydroxide as a catalyst, and performing hydrolytic condensation for 24-36 h at the temperature of 20-40 ℃; step three: and (3) carrying out rotary evaporation and concentration on the mixed solution to obtain viscous transparent liquid, washing with water for 3-5 times, and removing redundant catalyst to obtain the poly-silicon hydroxyl POSS. The invention synthesizes the polysilsesquioxane hydroxyl POSS which is not involved in hunting at home and abroad for a long time, the polysilsesquioxane hydroxyl POSS is directly synthesized by a one-step method, the synthesis method is simple and easy to operate, and the post-treatment of the product is simple. The poly-silicon hydroxyl POSS is directly synthesized by using tetrapropoxysilane in one step. Using Et4NOH/Me4NOH is used as a catalyst to synthesize the poly-silicon hydroxyl POSS at low temperature, and the operation is simple and the synthesis condition is mild. The method for synthesizing the polysilsesquioxane hydroxyl POSS has high yield and short time consumption.

Description

Synthesis method of poly-silicon hydroxyl POSS
Technical Field
The invention belongs to the technical field of POSS preparation, and particularly relates to a synthesis method of polysilsesquioxane hydroxyl POSS.
Background
Polyhedral Oligomeric Silsesquioxane (POSS for short) is a novel organic-inorganic hybrid material and has a special cage-shaped framework structure. The general formula of the Structure Is (SiO)1.5R) n (n-6.8.10.12), the most common of which is T8Type cage POSS. The POSS has a special cage-type framework structure consisting of alternate-Si-O-Si-bonds inside and is connected with a plurality of active or inert groups outside. The regular and special intramolecular hybrid structure makes it possess heat resistance, mechanical performance and organic matter reactivity of inorganic matter and is favorable to molecular design. POSS can be used for copolymerization with monomers to improve the performance of polymers, and is a very good modified material. Since it is itself oneThe POSS solves the problem of agglomeration when the traditional inorganic filler improves the polymer, has good improvement effect on a series of polymers, and obviously improves the mechanical property, the dielectric property, the heat resistance and other aspects. At present, no relevant reports on the synthesis of multi-silicon hydroxyl POSS exist at home and abroad.
Disclosure of Invention
The invention aims to solve the problem that polysilsesquioxane hydroxyl POSS is difficult to synthesize at present and provides a synthesis method of polysilsesquioxane hydroxyl POSS.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing multi-silicon hydroxyl POSS comprises the following steps:
the method comprises the following steps: mixing the methanol solution and tetrapropoxysilane;
step two: adding tetramethylammonium hydroxide/ethylammonium hydroxide as a catalyst, and performing hydrolytic condensation for 24-36 h at the temperature of 20-40 ℃;
step three: and (3) carrying out rotary evaporation and concentration on the mixed solution to obtain viscous transparent liquid, washing with water for 3-5 times, and removing redundant catalyst to obtain the poly-silicon hydroxyl POSS.
Compared with the prior art, the invention has the beneficial effects that: the invention synthesizes the polysilsesquioxane hydroxyl POSS which is not involved in hunting at home and abroad for a long time, the polysilsesquioxane hydroxyl POSS is directly synthesized by a one-step method, the synthesis method is simple and easy to operate, and the post-treatment of the product is simple. The poly-silicon hydroxyl POSS is directly synthesized by using tetrapropoxysilane in one step. Using Et4NOH/Me4NOH is used as a catalyst to synthesize the poly-silicon hydroxyl POSS at low temperature, and the operation is simple and the synthesis condition is mild. The method for synthesizing the polysilsesquioxane hydroxyl POSS has high yield and short time consumption.
Drawings
FIG. 1 is an infrared spectrum of a synthetic polysilsesquioxane hydroxyl POSS;
FIG. 2 is a mass spectrum of synthetic polysilsesquioxane hydroxyl POSS.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
The first embodiment is as follows: the present embodiment describes a method for synthesizing polysilsesquioxane hydroxyposs, the method comprising the steps of:
the method comprises the following steps: mixing the methanol solution and tetrapropoxysilane; tetrapropoxysilane is used as a coupling agent and can be used for synthesizing polysilsesquioxane POSS with methanol in one step;
step two: adding tetramethylammonium hydroxide/ethylammonium hydroxide as a catalyst, and performing hydrolytic condensation for 24-36 h at the temperature of 20-40 ℃;
step three: and (3) carrying out rotary evaporation and concentration on the mixed solution to obtain viscous transparent liquid, washing with water for 3-5 times, and removing redundant catalyst to obtain the poly-silicon hydroxyl POSS.
The second embodiment is as follows: in the first step of the method for synthesizing polysilsesquioxane hydroxyposs, the methanol solution is analytically pure.
The third concrete implementation mode: in the first step of the method for synthesizing polysilsesquioxane hydroxyPOSS, the mass-to-volume ratio of the tetrapropoxysilane to the methanol solution is 22.4 g: 100 ml.
The fourth concrete implementation mode: in the second step of the method for synthesizing polysilcon hydroxyl POSS, the volume ratio of the tetramethylammonium hydroxide/ethylammonium hydroxide to the methanol solution is 3: 10.
the fifth concrete implementation mode: in the second step of the method for synthesizing poly-silicon hydroxyl POSS according to the first embodiment, the adding speed of the tetramethylammonium hydroxide/ethylammonium hydroxide is 20 drops/min.
The sixth specific implementation mode: in the third step, the temperature of the rotary evaporation concentration is 40-60 ℃, and the volume of the rotary evaporation is 1/4-1/2 of the original volume.
The seventh embodiment: in the third step, acetone or THF is added to the mixed solution from which the catalyst is removed to precipitate, and the solution is separated to obtain a white viscous liquid, that is, the polysilsesquioxane.
The specific implementation mode is eight: in the method for synthesizing polysilsesquioxane hydroxyl POSS according to the seventh embodiment, the volume ratio of the acetone or THF to the mixed solution is 1-2: 1.
example 1:
a method for synthesizing multi-silicon hydroxyl POSS comprises the following steps:
the method comprises the following steps: 100ml of methanol solution was mixed with 22.4g of tetrapropoxysilane; tetrapropoxysilane is used as a coupling agent, and polysilxyl POSS can be synthesized in one step through hydrolytic condensation; the methanol solution was analytically pure.
Step two: adding 30ml of tetramethyl/ethyl ammonium hydroxide as a catalyst, and carrying out hydrolytic condensation for 24-36 h at the temperature of 20-40 ℃; the addition rate of the tetramethylammonium hydroxide/ethylammonium hydroxide was 20 drops/min.
Step two: and (3) carrying out rotary evaporation and concentration on the mixed solution to obtain 30ml of viscous transparent liquid, washing with water for 3-5 times, removing redundant catalyst, adding 30-60 ml of acetone or THF for precipitation, and separating liquid to obtain white viscous liquid, namely the polysilcon hydroxyl POSS. The temperature of the rotary evaporation concentration is 40-60 ℃.
FIG. 1 is an infrared spectrum of a synthetic polysilsesquioxane hydroxyl POSS; 3450cm-1The left and right peaks are stretching vibration peaks of-OH; 2930, 2850cm-1The left and right peaks are-CH2-a stretching vibration peak indicating the presence of incompletely hydrolyzed tetrapropoxysilane in the product; 1115cm-1The left and right peaks are stretching vibration peaks of-Si-O-Si and are also characteristic peaks of the cage-shaped framework; thus, polysiloxyl POSS is present in the product. FIG. 2 is a mass spectrum of synthetic polysilsesquioxane hydroxyl POSS. The peak having m/z of 574.5 is octasilylhydroxy [ POSS + Na ]]+Peak(s). Further evidence that polysilsesquioxane hydroxyl POSS is present in the product, consistent with the infrared results.

Claims (5)

1. A method for synthesizing multi-silicon hydroxyl POSS is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: mixing the methanol solution and tetrapropoxysilane; the methanol solution is analytically pure; the mass-volume ratio of the tetrapropoxysilane to the methanol solution is 22.4 g: 100 ml;
step two: adding tetramethylammonium hydroxide/ethylammonium hydroxide as a catalyst, and performing hydrolytic condensation for 24-36 h at the temperature of 20-40 ℃; the volume ratio of the tetramethylammonium hydroxide/ethyl ammonium hydroxide to the methanol solution is 3: 10;
step three: and (3) carrying out rotary evaporation and concentration on the mixed solution to obtain viscous transparent liquid, washing with water for 3-5 times, and removing redundant catalyst to obtain the poly-silicon hydroxyl POSS.
2. The method of synthesizing multi-silicon hydroxyl POSS as claimed in claim 1 wherein: in the second step, the adding speed of the tetramethyl/ethyl ammonium hydroxide is 20 drops/min.
3. The method of synthesizing multi-silicon hydroxyl POSS as claimed in claim 1 wherein: in the third step, the temperature of the rotary evaporation concentration is 40-60 ℃, and the volume of the rotary evaporation is 1/4-1/2 of the original volume.
4. The method of synthesizing multi-silicon hydroxyl POSS as claimed in claim 1 wherein: and in the third step, adding acetone or THF into the mixed solution without the catalyst for precipitation, and separating to obtain white viscous liquid, namely the polysilsesquioxane hydroxyl POSS.
5. The method of claim 4 for synthesizing a polysilcon hydroxyl POSS, wherein the method comprises the steps of: the volume ratio of the acetone or the THF to the mixed solution is 1-2: 1.
CN201910854383.1A 2019-09-10 2019-09-10 Synthesis method of poly-silicon hydroxyl POSS Active CN110483777B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910854383.1A CN110483777B (en) 2019-09-10 2019-09-10 Synthesis method of poly-silicon hydroxyl POSS

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910854383.1A CN110483777B (en) 2019-09-10 2019-09-10 Synthesis method of poly-silicon hydroxyl POSS

Publications (2)

Publication Number Publication Date
CN110483777A CN110483777A (en) 2019-11-22
CN110483777B true CN110483777B (en) 2022-02-08

Family

ID=68557239

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910854383.1A Active CN110483777B (en) 2019-09-10 2019-09-10 Synthesis method of poly-silicon hydroxyl POSS

Country Status (1)

Country Link
CN (1) CN110483777B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6660823B1 (en) * 1998-03-03 2003-12-09 The United States Of America As Represented By The Secretary Of The Air Force Modifying POSS compounds
CN1513858A (en) * 2003-08-20 2004-07-21 胡立江 Preparation method of multihydroxy sesqui siloxane
CN105254661A (en) * 2015-10-23 2016-01-20 航天材料及工艺研究所 Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof
CN108948073A (en) * 2018-08-15 2018-12-07 哈尔滨工业大学 A kind of preparation method of polyhydroxy sesquialter silane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6660823B1 (en) * 1998-03-03 2003-12-09 The United States Of America As Represented By The Secretary Of The Air Force Modifying POSS compounds
CN1513858A (en) * 2003-08-20 2004-07-21 胡立江 Preparation method of multihydroxy sesqui siloxane
CN105254661A (en) * 2015-10-23 2016-01-20 航天材料及工艺研究所 Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof
CN108948073A (en) * 2018-08-15 2018-12-07 哈尔滨工业大学 A kind of preparation method of polyhydroxy sesquialter silane

Also Published As

Publication number Publication date
CN110483777A (en) 2019-11-22

Similar Documents

Publication Publication Date Title
CN102432883B (en) Preparation method of phenyl-vinyl silicon oil
CN111072973B (en) Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant
CN105254661A (en) Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof
CN102702532B (en) Method for preparing organosilicone hybrid resin and power type encapsulating material for light-emitting diodes (LED) thereof and application
CN101880396A (en) Preparation method of organic silicon rubber for encapsulating LED being convenient for vacuum defoamation
CN106750312B (en) Phenyl DT (bismuth telluride) silicone resin and preparation method thereof
CN102898650B (en) MTQ silicon resin with T-chain unit containing phenyl and preparation method thereof
CN102250355B (en) Fluorine- and epoxide group-containing polysiloxane, and preparation method and application thereof
CN104530645B (en) Organic fluorine modified epoxy/nano SiO2 LED (light-emitting diode) composite packaging material and preparation method thereof
CN109134864B (en) Trapezoidal polysilsesquioxane derivative and preparation method thereof
CN101942201A (en) Room-temperature vulcanized antiflaming single-component dealcoholization-type silicone rubber sealant and preparation method thereof
KR20040029277A (en) Basket type silsesquioxane resin having functional group and method of producing the same
CN110483777B (en) Synthesis method of poly-silicon hydroxyl POSS
CN114456128B (en) Application of isovanillin epoxy resin monomer in preparation of silicon-containing polymer
CN107118351A (en) Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application
CN108976423A (en) A kind of cage-type silsesquioxane of cyano-containing and preparation method thereof
CN103194063B (en) Trapezoidal polysiloxane modified thermosetting resin and preparation method thereof
CN110229339B (en) Phenyl vinyl siloxane resin, high-refractive-index LED packaging silicon resin composition and preparation method thereof
CN115612104A (en) Production process of electronic grade 107 with low ring body content
KR20130125224A (en) Ladder-type thiol-based silsesquioxane polymer and method for preparing the same
CN103059573A (en) Inorganic/organic hybridization nanometer composite resin and light-emitting diode (LED) packaging materials prepared by the same
CN111205462A (en) Preparation method of silicone resin containing perfluor cyclobutyl aryl ether structure
CN103435807A (en) Method for preparing odorless and transparent 107 glue at ordinary pressure
CN110256676B (en) Phenyl hydrogen-containing siloxane resin, high-refractive-index LED packaging silicon resin composition and preparation method thereof
CN108948073B (en) Preparation method of polyhydroxy silsesquioxane

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant