CN109180944A - Polysilsesquioxane of cage modle containing chlorine and preparation method thereof - Google Patents
Polysilsesquioxane of cage modle containing chlorine and preparation method thereof Download PDFInfo
- Publication number
- CN109180944A CN109180944A CN201811054692.2A CN201811054692A CN109180944A CN 109180944 A CN109180944 A CN 109180944A CN 201811054692 A CN201811054692 A CN 201811054692A CN 109180944 A CN109180944 A CN 109180944A
- Authority
- CN
- China
- Prior art keywords
- integer
- cage modle
- polysilsesquioxane
- method described
- solvent
- 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.)
- Granted
Links
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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 kind of polysilsesquioxane of cage modle containing chlorine, shown in formula I.The present invention polysilsesquioxane of cage modle containing chlorine has preferable anti-flammability, can be used for the composite materials such as epoxy resin, polyurethane and polystyrene.
Description
Technical field
The present invention relates to a kind of siloxanes more particularly to a kind of cage modle polysilsesquioxane, with and preparation method thereof.
Background technique
Cage modle polysilsesquioxane (POSS) is a kind of novel nano-material, is developed by the Air Force Research Laboratory, is used
In the polyhedral structure that high-performance polymer material, the kernel of POSS are alternately connected and composed by Si-O, polyhedral apex angle is had
Take base.Although POSS is inorganic constituents, scale is small, has for organic substituent, so, POSS and polymer material
Compatibility is fine, and polymer/POSS composite material has excellent comprehensive performance, and being mainly characterized in that: (1) raising composite material makes
Use temperature；(2) mechanical property of composite material is improved；(3) anti-flammability of composite material is improved；(5) improve composite material surface
Performance, etc..
POSS itself has certain anti-flammability, after polymer adds POSS material, as content improves, when reaching one
After definite value, the oxygen index (OI) (LOI) of material will be significantly improved, nevertheless, the anti-flammability efficiency of POSS is not high.
Summary of the invention
It is an object of the present invention to provide a kind of polysilsesquioxanes of cage modle containing chlorine, to further increase its anti-flammability
Energy.
It is another object of the present invention to provide a kind of preparation methods of polysilsesquioxane of cage modle containing chlorine.
For achieving the above object, a kind of polysilsesquioxane of cage modle containing chlorine provided by the invention, shown in formula I
Wherein,
R1 is CnH2n1+1-m1Clm1, 1 < m1 < 2n1, the integer that n1 is 2~18；
R2 is CnH2n2+1-m2Clm2, 1 < m2 < 2n2, the integer that n2 is 2~18；
R3 is CnH2n3+1-m3Clm3, 1 < m3 < 2n3, the integer that n3 is 2~18；
R4 is CnH2n4+1-m4Clm4, 1 < m4 < 2n4, the integer that n4 is 2~18；
R5 is CnH2n5+1-m5Clm5, 1 < m5 < 2n5, the integer that n5 is 2~18；
R6 is CnH2n6+1-m6Clm6, 1 < m6 < 2n6, the integer that n6 is 2~18；
R7 is CnH2n7+1-m7Clm7, 1 < m7 < 2n7, the integer that n7 is 2~18；
R8 is CnH2n8+1-m8Clm8, 1 < m8 < 2n8, the integer that n8 is 2~18.
Cage modle polysilsesquioxane of the invention is applied to epoxy resin, polyurethane, polystyrene and gathers as fire retardant
In the materials such as ester, flame retardant property is improved.
A kind of preparation method of the polysilsesquioxane of cage modle containing chlorine, comprising:
In a solvent by the dissolution of compound shown in Formula II, it is passed through chlorine, after reacting under ultraviolet light, is passed through air,
Reaction is terminated, solvent is removed, obtains cage modle polysilsesquioxane；
Wherein R base is saturated alkyl CnH2n+1, n be 2~18 integer.
Solvent for use is the halogenated hydrocarbons of C1~C4, such as: but it is not limited only to carbon tetrachloride, dichloroethanes and tetrachloroethanes,
Preferential selection carbon tetrachloride.
The temperature of reaction is 20 DEG C~90 DEG C, preferential 30 DEG C~80 DEG C of selection.
The time of reaction is 0.5 hour~24 hours.
Ultraviolet light is the light of wavelength 100nm~400nm, can be generated by mercury lamp with light sources such as xenon lamp and LED.
Technical solution of the present invention realize the utility model has the advantages that
Cage modle polysilsesquioxane provided by the invention, by increasing substituent group in cage modle polysilsesquioxane structure
Chlorine can be widely applied to each middle polymer composites so that anti-flammability significantly improves, such as: epoxy resin, gathers polyurethane
Styrene, polyester etc..
Specific embodiment
Technical solution of the present invention described in detail below.The embodiment of the present invention be merely illustrative of the technical solution of the present invention and
It is unrestricted, although being described the invention in detail referring to preferred embodiment, those skilled in the art should understand that,
Can with modification or equivalent replacement of the invented technical scheme, without departing from the spirit and scope of the technical solution of the present invention,
It should all cover within the scope of the claims of the present invention.
Embodiment 1
200 gram of eight isobutyl group cage modle eight polysilsesquioxane is dissolved in 800 grams of carbon tetrachloride, chlorine is passed through, uses high pressure
Mercury lamp irradiation maintains 60 DEG C to react 8 hours, is passed through air and terminates reaction, steam solvent, obtain 436 grams (being denoted as: POSS1), contains chlorine
Amount 55%.
Embodiment 2
200 grams of octaethyl cage modle eight polysilsesquioxanes are dissolved in 800 grams of dichloroethanes, chlorine is passed through, uses high-pressure mercury
Lamp irradiation, maintain 40 DEG C react 5 hours, be passed through air terminate reaction, steam solvent, 368 grams (being denoted as: POSS2), chlorinty
47%.
Embodiment 3
200 gram of eight isobutyl group cage modle eight polysilsesquioxane is dissolved in 800 grams of carbon tetrachloride, chlorine is passed through, uses high pressure
Mercury lamp irradiation, maintain 30 DEG C react 4 hours, be passed through air terminate reaction, steam solvent, 381 grams (being denoted as: POSS3), contain chlorine
Amount 48%.
Embodiment 4
200 gram of eight n-octadecane base cage modle eight polysilsesquioxane is dissolved in 800 grams of carbon tetrachloride, chlorine is passed through, is used
High voltage mercury lamp irradiation maintains 60 DEG C to react 1 hour, is passed through air and terminates reaction, steams solvent, obtain 332 grams (being denoted as: POSS4),
Chlorinty 42%.
Embodiment 5
70 parts of polypropylene glycol PPG600 are uniformly mixed with 30 parts of cage modle eight polysilsesquioxanes, are polymerize with 30 parts of PM-200
MDI is sufficiently mixed, and pours into 100mm × 6.5mm × 3.2mm batten, and room temperature is down to, according to ASTM D- in 70 DEG C i.e. heat 24 hours
2863 tests oxygen index (OI) (LOI), referring to table 1.
Table 1
Claims (10)
1. a kind of cage modle polysilsesquioxane, shown in formula I
Wherein,
R1 is CnH2n1+1-m1Clm1, 1 < m1 < 2n1, the integer that n1 is 2~18；
R2 is CnH2n2+1-m2Clm2, 1 < m2 < 2n2, the integer that n2 is 2~18；
R3 is CnH2n3+1-m3Clm3, 1 < m3 < 2n3, the integer that n3 is 2~18；
R4 is CnH2n4+1-m4Clm4, 1 < m4 < 2n4, the integer that n4 is 2~18；
R5 is CnH2n5+1-m5Clm5, 1 < m5 < 2n5, the integer that n5 is 2~18；
R6 is CnH2n6+1-m6Clm6, 1 < m6 < 2n6, the integer that n6 is 2~18；
R7 is CnH2n7+1-m7Clm7, 1 < m7 < 2n7, the integer that n7 is 2~18；
R8 is CnH2n8+1-m8Clm8, 1 < m8 < 2n8, the integer that n8 is 2~18.
2. cage modle polysilsesquioxane according to claim 1 is used for epoxy resin, polyurethane, polyphenyl second as fire retardant
In the materials such as alkene and polyester.
3. a kind of fire retardant, including cage modle polysilsesquioxane described in claim 1.
4. a kind of method for preparing cage modle polysilsesquioxane described in claim 1, comprising:
In a solvent by the dissolution of compound shown in Formula II, it is passed through chlorine, after reacting under ultraviolet light, is passed through air, terminated
Reaction removes solvent, obtains cage modle polysilsesquioxane；
Wherein R base is saturated alkyl CnH2n+1, n be 2~18 integer.
5. according to the method described in claim 4, it is characterized in that the solvent is the halogenated hydrocarbons of C1~C4.
6. according to the method described in claim 4, it is characterized in that the solvent is selected from carbon tetrachloride, dichloroethanes and four
The one or more of chloroethanes.
7. according to the method described in claim 4, it is characterized in that the reaction temperature is 20 DEG C~90 DEG C.
8. according to the method described in claim 4, it is characterized in that the reaction temperature is 30 DEG C~80 DEG C.
9. according to the method described in claim 4, it is characterized in that the reaction time is 0.5 hour~24 hours.
10. according to the method described in claim 4, it is characterized in that the wavelength of the ultraviolet light is 100nm~400nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811054692.2A CN109180944B (en) | 2018-09-10 | 2018-09-10 | Chlorine-containing cage type polysilsesquioxane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811054692.2A CN109180944B (en) | 2018-09-10 | 2018-09-10 | Chlorine-containing cage type polysilsesquioxane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109180944A true CN109180944A (en) | 2019-01-11 |
| CN109180944B CN109180944B (en) | 2020-12-08 |
Family
ID=64915719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811054692.2A Active CN109180944B (en) | 2018-09-10 | 2018-09-10 | Chlorine-containing cage type polysilsesquioxane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109180944B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924464A (en) * | 2016-05-18 | 2016-09-07 | 上海大学 | Octa-imidazolyl POSS room temperature ionic liquid and preparation method thereof |
| CN107366159A (en) * | 2017-08-29 | 2017-11-21 | 中国科学院长春应用化学研究所 | A kind of preparation method polymer-modified POSS |
-
2018
- 2018-09-10 CN CN201811054692.2A patent/CN109180944B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924464A (en) * | 2016-05-18 | 2016-09-07 | 上海大学 | Octa-imidazolyl POSS room temperature ionic liquid and preparation method thereof |
| CN107366159A (en) * | 2017-08-29 | 2017-11-21 | 中国科学院长春应用化学研究所 | A kind of preparation method polymer-modified POSS |
Non-Patent Citations (1)
| Title |
|---|
| XIU QIANG；FANG CHEN；XIAO-YAN MA: "Star-Shaped POSS–Methacrylate Copolymers with Phenyl–Triazole as Terminal Groups, Synthesis, and the Pyrolysis Analysis", 《J. APPL. POLYM. SCI.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109180944B (en) | 2020-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102179230B (en) | Preparation method of magnetized silicon dioxide aerogel | |
| Wu et al. | Morphological changes of limestone sorbent particles during carbonation/calcination looping cycles in a thermogravimetric analyzer (TGA) and reactivation with steam | |
| Xu et al. | Fibrous aerogels with tunable superwettability for high-performance solar-driven interfacial evaporation | |
| CN109037550A (en) | A kind of method that Organoclay minerals prepare lithium battery coating diaphragm with polyvinylidene blending | |
| CN108667339A (en) | A kind of fiber base friction nanometer power generator of in-situ polymerization surface modification and its preparation | |
| TW200904909A (en) | Modified expansible graphite by silane modifying agent and producing method thereof | |
| CN104098905A (en) | Strong elastic phenyl organic silicone resin for LED lens and preparation method thereof | |
| CN107936652A (en) | Anti-fog haze low-carbon health coating | |
| Smitha et al. | Transparent and Hydrophobic MTMS/GPTMS Hybrid Aerogel Monoliths and Coatings by Sol‐Gel Method: A Viable Remedy for Oil‐Spill Cleanup | |
| CN109772263A (en) | Utilize cation exchange modified zeolite adsorbent method, zeolite adsorbents and application | |
| CN109180944A (en) | Polysilsesquioxane of cage modle containing chlorine and preparation method thereof | |
| Han et al. | Synergistic effects of ladder and cage structured phosphorus-containing POSS with tetrabutyl titanate on flame retardancy of vinyl epoxy resins | |
| CN111548112A (en) | Water purification type baking-free ceramsite and preparation method thereof | |
| CN104497314A (en) | Preparation method of low-phenyl hydrogen-containing silicone oil | |
| CN107083087A (en) | A kind of environment-friendly diatom ooze ornament materials and preparation method thereof | |
| Mei et al. | Silica–chitosan composite aerogels for thermal insulation and adsorption | |
| CN104226275B (en) | Hollow microsphere based on methacryloxy cage-type silsesquioxane and its preparation method and application | |
| CN113388059A (en) | High-refractive-index photocuring resin composition with oxazolidinone structure, preparation method thereof, and thiophenyl ether photosensitive monomer and intermediate thereof | |
| CN107880695A (en) | A kind of novel heat insulation coating | |
| CN107416847A (en) | A kind of aerosil of thienyl-containing group and preparation method thereof | |
| CN108774337B (en) | Hydrophobic modification method of melamine sponge, product and application thereof | |
| CN109718726B (en) | Production process of amphiphilic silica-chitosan composite aerogel | |
| Meti et al. | Evolutionary Progress of Silica Aerogels and Their Classification Based on Composition: An Overview | |
| Zhang et al. | Universality of mesoporous coal gasification slag for reinforcement and deodorization in four common polymers | |
| CN104984564B (en) | A kind of can selfreparing water-oil separating material and preparation method thereof |
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 | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Chlorine containing cage polysilsesquioxane and its preparation method Effective date of registration: 20210712 Granted publication date: 20201208 Pledgee: Agricultural Bank of China Limited by Share Ltd. South Lake branch Pledgor: ZHEJIANG RONGTAI TECHNICAL INDUSTRY Co.,Ltd. Registration number: Y2021330000875 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230619 Granted publication date: 20201208 Pledgee: Agricultural Bank of China Limited by Share Ltd. South Lake branch Pledgor: ZHEJIANG RONGTAI TECHNICAL INDUSTRY CO.,LTD. Registration number: Y2021330000875 |