CN109180944B - Chlorine-containing cage type polysilsesquioxane and preparation method thereof - Google Patents
Chlorine-containing cage type polysilsesquioxane and preparation method thereof Download PDFInfo
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- CN109180944B CN109180944B CN201811054692.2A CN201811054692A CN109180944B CN 109180944 B CN109180944 B CN 109180944B CN 201811054692 A CN201811054692 A CN 201811054692A CN 109180944 B CN109180944 B CN 109180944B
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
A chlorine-containing cage type polysilsesquioxane is shown as a formula I. The chlorine-containing cage type polysilsesquioxane has better flame retardance and can be used for composite materials such as epoxy resin, polyurethane, polystyrene and the like.
Description
Technical Field
The invention relates to siloxane, in particular to cage type polysilsesquioxane and a preparation method thereof.
Background
Cage type Polysilsesquioxane (POSS) is a novel nano material, is developed by American air force research laboratory and is used for high-performance polymer materials, the inner core of the POSS is of a polyhedral structure formed by alternately connecting Si and O, and the vertex angle of the polyhedron is provided with a substituent. Although POSS is an inorganic component, the POSS has small scale and is used for an organic substituent, so that the POSS has good compatibility with a polymer material, and the polymer/POSS composite material has excellent comprehensive performance and is mainly characterized in that: (1) the use temperature of the composite material is increased; (2) the mechanical property of the composite material is improved; (3) the flame retardance of the composite material is improved; (5) improve the surface properties of the composite, and the like.
The POSS has certain flame retardance, when the POSS material is added into the polymer, the oxygen index (LOI) of the material is obviously improved along with the increase of the content of the POSS material after reaching a certain value, and the flame retardance efficiency of the POSS is not high.
Disclosure of Invention
One object of the present invention is to provide a chlorine-containing cage type polysilsesquioxane to further improve the flame retardant property thereof.
The invention also aims to provide a preparation method of the chlorine-containing cage type polysilsesquioxane.
In order to achieve the purpose, the invention provides chlorine-containing cage type polysilsesquioxane which is shown as a formula I
Wherein the content of the first and second substances,
r1 is CnH2n1+1-m1Clm1M1 is more than 1 and less than 2n1, and n1 is an integer of 2-18;
r2 is CnH2n2+1-m2Clm2M2 is more than 1 and less than 2n2, and n2 is an integer of 2-18;
r3 is CnH2n3+1-m3Clm3M3 is more than 1 and less than 2n3, and n3 is an integer of 2-18;
r4 is CnH2n4+1-m4Clm4M4 is more than 1 and less than 2n4, and n4 is an integer of 2-18;
r5 is CnH2n5+1-m5Clm5M5 is more than 1 and less than 2n5, and n5 is an integer of 2-18;
r6 is CnH2n6+1-m6Clm6M6 is more than 1 and less than 2n6, and n6 is an integer of 2-18;
r7 is CnH2n7+1-m7Clm7M7 is more than 1 and less than 2n7, and n7 is an integer of 2-18;
r8 is CnH2n8+1-m8Clm8M8 is more than 1 and less than 2n8, and n8 is an integer of 2-18.
The cage type polysilsesquioxane provided by the invention is used as a flame retardant, is applied to materials such as epoxy resin, polyurethane, polystyrene and polyester, and improves the flame retardant property.
A preparation method of chlorine-containing cage type polysilsesquioxane comprises the following steps:
dissolving a compound shown as a formula II in a solvent, introducing chlorine, introducing air after reacting under ultraviolet irradiation, terminating the reaction, and removing the solvent to obtain cage-type polysilsesquioxane;
in which the radical R is a saturated alkyl radical CnH2n+1And n is an integer of 2 to 18.
The solvent is halogenated hydrocarbon of C1-C4, such as: but is not limited to carbon tetrachloride, dichloroethane, tetrachloroethane, etc., and carbon tetrachloride is preferred.
The reaction temperature is 20-90 deg.C, preferably 30-80 deg.C.
The reaction time is 0.5 to 24 hours.
The ultraviolet light is light having a wavelength of 100nm to 400nm and can be generated by a mercury lamp, a xenon lamp, an LED or the like.
The technical scheme of the invention has the following beneficial effects:
the cage type polysilsesquioxane provided by the invention has the advantages that the flame retardance is obviously improved by adding the substituent chlorine to the structure of the cage type polysilsesquioxane, and the cage type polysilsesquioxane can be widely applied to various polymer composite materials, such as: epoxy, polyurethane, polystyrene, polyester, and the like.
Detailed Description
The technical solution of the present invention is described in detail below. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
200 g of octaisobutyl cage octapolysilsesquioxane is dissolved in 800 g of carbon tetrachloride, chlorine is introduced, the mixture is irradiated by a high-pressure mercury lamp, the reaction is maintained at 60 ℃ for 8 hours, air is introduced to stop the reaction, and the solvent is evaporated to obtain 436 g (shown as POSS1) with the chlorine content of 55 percent.
Example 2
200 g of octaethyl cage octasilsesquioxane is dissolved in 800 g of dichloroethane, chlorine gas is introduced, the mixture is irradiated by a high-pressure mercury lamp, the reaction is maintained at 40 ℃ for 5 hours, air is introduced to stop the reaction, and 368 g (recorded as POSS2) of the solvent is evaporated out, wherein the chlorine content is 47%.
Example 3
200 g of octaisobutyl cage octapolysilsesquioxane is dissolved in 800 g of carbon tetrachloride, chlorine is introduced, the mixture is irradiated by a high-pressure mercury lamp, the reaction is maintained at 30 ℃ for 4 hours, air is introduced to stop the reaction, 381 g of solvent (marked as POSS3) is evaporated, and the chlorine content is 48 percent.
Example 4
200 g of octa-n-octadecyl cage-type octapolysilsesquioxane is dissolved in 800 g of carbon tetrachloride, chlorine gas is introduced, the mixture is irradiated by a high-pressure mercury lamp, the reaction is maintained at 60 ℃ for 1 hour, air is introduced to stop the reaction, and the solvent is evaporated to obtain 332 g (marked as POSS4) with the chlorine content of 42 percent.
Example 5
70 parts of polypropylene glycol PPG600 and 30 parts of cage octasilsesquioxane were mixed uniformly, thoroughly mixed with 30 parts of PM-200 polymeric MDI, cast into 100 mm. times.6.5 mm. times.3.2 mm bars, heated at 70 ℃ for 24 hours, cooled to room temperature, and tested for oxygen index (LOI) according to ASTM D-2863, see Table 1.
TABLE 1
Claims (7)
1. A method of preparing a cage polysilsesquioxane comprising:
dissolving a compound shown as a formula II in a solvent, introducing chlorine, introducing air after reacting under ultraviolet irradiation, terminating the reaction, and removing the solvent to obtain cage type polysilsesquioxane shown as a formula I;
in which the radical R is a saturated alkyl radical CnH2n+1N is an integer of 2 to 18;
wherein the content of the first and second substances,
r1 is CnH2n1+1-m1Clm1，1<m1<2n1, wherein n1 is an integer of 2-18;
r2 is CnH2n2+1-m2Clm2，1<m2<2n2, wherein n2 is an integer of 2-18;
r3 is CnH2n3+1-m3Clm3，1<m3<2n3, wherein n3 is an integer of 2-18;
r4 is CnH2n4+1-m4Clm4，1<m4<2n4, wherein n4 is an integer of 2-18;
r5 is CnH2n5+1-m5Clm5，1<m5<2n5, wherein n5 is an integer of 2-18;
r6 is CnH2n6+1-m6Clm6，1<m6<2n6, wherein n6 is an integer of 2-18;
r7 is CnH2n7+1-m7Clm7，1<m7<2n7, wherein n7 is an integer of 2-18;
r8 is CnH2n8+1-m8Clm8，1<m8<2n8, n8 is an integer of 2 to 18.
2. The method of claim 1, wherein the solvent is a halogenated hydrocarbon of C1-C4.
3. The method according to claim 1, wherein the solvent is selected from one or more of carbon tetrachloride, dichloroethane and tetrachloroethane.
4. The process according to claim 1, wherein the reaction temperature is 20 ℃ to 90 ℃.
5. The process according to claim 1, wherein the reaction temperature is from 30 ℃ to 80 ℃.
6. The process of claim 1, wherein the reaction time is from 0.5 to 24 hours.
7. The method of claim 1, wherein the ultraviolet light has a wavelength of 100nm to 400 nm.
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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 |
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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 (2)
| Title |
|---|
| Star-Shaped POSS–Methacrylate Copolymers with Phenyl–Triazole as Terminal Groups, Synthesis, and the Pyrolysis Analysis;Xiu Qiang；Fang Chen；Xiao-Yan Ma;《J. APPL. POLYM. SCI.》;20140815;第40652（1-9）页 * |
| 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.》.2014, * |
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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 |
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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 |