CN109369699B - Reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound and preparation method thereof - Google Patents
Reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound and preparation method thereof Download PDFInfo
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- CN109369699B CN109369699B CN201811298987.4A CN201811298987A CN109369699B CN 109369699 B CN109369699 B CN 109369699B CN 201811298987 A CN201811298987 A CN 201811298987A CN 109369699 B CN109369699 B CN 109369699B
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
Abstract
The invention relates to a reactive organosilicon flame retardant allylThe structure of the silicic acid trisilacyl alcohol ester compound is shown as the following formula:
Description
Technical Field
The invention relates to a reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound and a preparation method thereof, in particular to a reactive organosilicon flame retardant allyl tris { 1-methyl-1-sila-2, 6, 7-trioxabicyclo [2, 2, 2] octyl- (4) -methyleneoxy } silane compound and a preparation method thereof, wherein the compound is suitable for serving as a flame retardant for materials such as unsaturated resin, styrene, acrylate, polyester, polyamide, polyurethane, epoxy resin, polyolefin and the like.
Background
The wide application of flammable synthetic polymer materials drives the rapid development of the flame retardant industry; along with the continuous improvement of living standard and the continuous enhancement of consciousness of safety and environmental protection of people, higher requirements are made on a flame retardant, the flame retardant efficiency is required, meanwhile, the safety, non-toxicity and environmental protection performance are better emphasized, the research and application of the organic silicon flame retardant cater to the social requirements, and particularly, the cage-shaped organic silicon derivative serving as the flame retardant has good thermal stability and good char formation property and has the function of preventing molten drops from causing secondary combustion, so that the cage-shaped organic silicon derivative becomes a popular research topic of the flame retardant which is halogen-free, environment-friendly, low-toxicity, high-temperature-resistant and efficient at present.
In addition, the flame retardants used in the current polymer materials are additive flame retardants and reactive flame retardants. Because of more or less incompatibility between the additive flame retardant and the polymer matrix, the additive flame retardant can escape, decompose and the like during processing, and the performance of the material is influenced. The reactive flame retardant is prepared by directly introducing flame retardant elements into a main chain or a side chain of a polymer in a copolymerization or grafting mode, so that the effect of improving the flame retardance can be achieved, the defect that an additive flame retardant migrates or volatilizes from the surface of the polymer can be overcome, the influence on the physical and chemical properties of the polymer is small, and the development prospect is good.
The invention discloses a reactive organosilicon flame retardant allyl silicic acid trisilicon alcohol ester compound and a preparation method thereof. The invention takes pentaerythritol methylsilicate and allyl trichlorosilane or allyl trimethoxy silane as raw materials, prepares the reaction type cage-shaped silicon compound by a one-step method, has simple process, less equipment investment, convenient operation and low cost, and is easy to convert into industrial production; the flame retardant has the advantages of high silicon content, high flame-retardant efficiency, good char formation, symmetrical structure, good compatibility with materials, no toxic gas generated in the combustion process and the like. In particular, the molecule has active allyl group which can be polymerized with the material to generate the bulk flame-retardant polymer material, and the flame retardant does not migrate and does not deteriorate the physical properties of the material due to the addition of the flame retardant, so the flame retardant has very good application and development prospects.
Disclosure of Invention
One of the purposes of the invention is to provide a reactive organosilicon flame retardant allyl silicic acid trisilicon caged alcohol ester compound which has the advantages of high silicon content, symmetrical structure, moderate polarity, good compatibility with materials, capability of being used as a reactive flame retardant, capability of being used as an additive flame retardant, no toxic or harmful gas generation in the combustion process and the like; the flame retardant is suitable for being used as a flame retardant for unsaturated resin, styrene, acrylate, polyester, polyamide, polyurethane, epoxy resin, polyvinyl alcohol, polyolefin and other materials, and can overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound is characterized in that the structure of the compound is shown as the following formula:
the invention also aims to provide a preparation method of the reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound, which has the advantages of simple process, easy large-scale production, cheap and easily-obtained raw materials, low equipment investment and low cost.
The method comprises the following steps:
adding an organic solvent and methyl pentaerythritol silicate into a reactor which is provided with a stirrer, a thermometer and a reflux condenser and is connected with a drying and hydrogen chloride absorption device, heating to 60 ℃, starting to dropwise add allyl trichlorosilane under the protection of nitrogen, heating to 120-150 ℃, carrying out heat preservation reaction for 11-15h after finishing dripping, adjusting the pH to 6.5-8 by using an acid-binding agent, cooling to 25 ℃, filtering, washing a filter cake by using cold water with the volume of 2 times milliliter of the theoretical mass gram of the product, and drying to obtain white solid allyl silicic acid trisilicon ester.
The method can also comprise the following steps:
adding pentaerythritol methylsilicate, organic solvent and allyltrimethoxysilane into a reactor provided with a stirrer, a thermometer and a fractionating device, heating to 100 ℃, starting reflux, gradually heating to 120-150 ℃ in reflux, keeping the temperature for reaction for 14-18h, controlling the temperature at the top of the tower to be not higher than 65 ℃ in the whole process, leading the separated methanol to reach the theoretical amount, stopping the reaction, cooling to 25 ℃, filtering, washing a filter cake with 60 ml of cold water, and drying to obtain white solid allylsilicic acid trisilicon alcohol ester
The organic solvent is ethylene glycol diethyl ether, tetrachloroethane, diethylene glycol dimethyl ether or anisole, and the volume milliliter number of the organic solvent is 3 to 5 times of the mass number of the pentaerythritol methylsilicate.
The acid-binding agent is triethylamine, pyridine or N, N-dimethylaniline.
The methyl pentaerythrityl silicate is 1-methyl-1-sila-2, 6, 7-trioxa-4-hydroxymethyl bicyclo [2, 2, 2] octane, and the structure of the methyl pentaerythrityl silicate is shown as the following formula:
the reaction type organosilicon flame retardant allyl silicic acid trisilicon cage alcohol ester compound is a white solid, and the decomposition temperature is as follows: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The product is obtainedThe flame retardant has a ratio of 85.2-92.6%, and is suitable for use as a flame retardant for materials such as unsaturated resins, styrene, acrylates, polyesters, polyamides, polyurethanes, epoxy resins, polyolefins, and the like. The preparation principle of the phenyl silicic acid trisilicon caged alcohol ester compound serving as the organic silicon flame-retardant charring agent is as follows:
compared with the prior art, the invention has the beneficial effects that:
the organic silicon flame retardant allyl silicic acid trisilicon alcohol ester belongs to a multi-cage polysilicone compound, and has the advantages of high silicon content, high flame retardant efficiency, good symmetry of cage ring structure, stable product, high decomposition temperature and good processing performance; can be used as a reaction type flame retardant and an additive type flame retardant, and has wide application range.
The organic silicon flame retardant allyl silicic acid trisilicon caged alcohol ester compound has good char forming property, belongs to a high-efficiency environment-friendly flame retardant char forming agent, and has better char forming and melting and dripping prevention functions.
The preparation method of the organosilicon flame retardant allyl silicic acid trisilicon alcohol ester compound has the advantages of one-step reaction, simple process, less equipment investment, convenient operation, low cost and easy large-scale conversion and production.
Drawings
The following figures are presented to further illustrate the structure and performance characteristics of the product.
FIG. 1 is an infrared spectrum of trisilacagol allylsilicate; FIG. 1 shows, 3000cm-1is-CH ═ CH2A stretching vibration peak of the key; 2872cm-1Is the stretching vibration peak of the C-H bond; 1442cm-1Is the peak of bending vibration of the C-H bond; 1034cm-1Is the stretching vibration peak of the Si-O-C bond; 878cm-1Is the bending vibration peak of the Si-O-C bond; 754cm-1Is the stretching vibration peak of the Si-C bond; 1074.7cm-1Is the stretching vibration peak of the-C-O bond.
FIG. 2 is a nuclear magnetic spectrum of trisilacagyl allylsilicate; FIG. 2 shows the use of deuterated DMSO asIs a solvent, 0.10-0.12 is CH3-methyl hydrogen peak on Si; 1.0-1.06 is C-CH2Exocyclic methylene hydrogen peak on O-Si; 1.08-1.25 is Si-CH2-CH＝CH2The upper silicon-bonded methylene hydrogen peak; 3.5-3.6 is C-CH2A methylene peak in the ring on O-Si; 3.6-4.0 is Si-OCH2CH＝CH2Hydrogen peak on the olefinic bond; 2.5 is H in DMSO solvent2Hydrogen peak in O.
FIG. 3 is a differential thermogram of trisilacyl allylsilicate; FIG. 3 shows that weight loss begins when the temperature rises to around 355 ℃; when the temperature is heated to 380 ℃, the weight loss rate of the product reaches 50 percent; after the final temperature reached 800 ℃, there was still 21% residue, indicating that the synthesized product has good thermal stability properties.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solution of the present invention is further described below with reference to the specific embodiments.
Example 1 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a drying tube and a hydrogen chloride absorption device connected at the upper port, 0.15mol (26.40g) of pentaerythritol methylsilicate and 130ml of ethylene glycol diethyl ether are added, under the protection of nitrogen, the temperature is raised to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane is started to be dripped, after dripping is finished, the reflux is gradually raised to 120 ℃, the temperature is kept for reaction for 11h, the pH value is adjusted to 6.5-8 by a triethylamine acid-binding agent, the reaction is cooled to 25 ℃, the reaction solution is filtered, washed by 70ml of cold water and dried, and white solid allyl caged alcohol silicate is obtained, the decomposition temperature: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 85.3%.
Example 2 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a drying tube and a hydrogen chloride absorption device connected at the upper port, 0.155mol (27.28g) of pentaerythritol methylsilicate and 100ml of tetrachloroethane were added, under the protection of nitrogen, the temperature was raised to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane was started to be added dropwise, after the dropwise addition, the reflux was gradually raised to 130 ℃, the reaction was carried out for 12 hours, the pH was adjusted to 6.5-8 with a pyridine acid-binding agent, the reaction was cooled to 25 ℃, the reaction solution was filtered, washed with 70ml of cold water and dried to obtain white solid allyl trisilicate alcohol ester, the decomposition temperature of which was 6.5-8Degree: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 89.2%.
Example 3 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a drying tube and a hydrogen chloride absorption device connected at the upper port, 0.16mol (28.40g) of methyl pentaerythritol silicate and 100ml of diethylene glycol dimethyl ether are added, under the protection of nitrogen, the temperature is raised to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane is started to be dripped, after dripping is finished, the reflux is gradually raised to 140 ℃, the temperature is kept for reaction for 13h, the pH value is adjusted to 6.5-8 by a triethylamine acid-binding agent, the reaction is cooled to 25 ℃, and the reaction solution is filtered, washed by 70ml of cold water and dried to obtain white solid allyl trisilicon ester, the decomposition temperature of the white solid is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.2%.
Example 4 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and connected with a drying tube and a hydrogen chloride absorption device at the upper port, 0.165mol (29.04g) of methyl pentaerythritol silicate and 110ml of anisole are added, under the protection of nitrogen, the reflux is gradually heated to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane is started to be dripped, after the dripping is finished, the temperature is raised to 150 ℃, the reaction is kept for 13h, the pH value is adjusted to 6.5-8 by triethylamine acid-binding agent, the reaction is cooled to 25 ℃, the reaction solution is filtered, washed by 70ml of cold water and dried, and white solid allyl trisilicon alcohol ester is obtained, the decomposition temperature: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.1%.
Example 5 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a drying tube and a hydrogen chloride absorption device connected to the upper port, 0.17mol (29.92g) of pentaerythritol methylsilicate and 90ml of tetrachloroethane were added, under the protection of nitrogen, the temperature was raised to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane was started to be added dropwise, after the dropwise addition, the reflux was gradually raised to 140 ℃, the reaction was maintained for 15 hours, the pH was adjusted to 6.5-8 with a pyridine acid-binding agent, the reaction was cooled to 25 ℃, the reaction solution was filtered, washed with 70ml of cold water and dried to obtain white solid allyl trisilicate alcohol ester, the decomposition temperature thereof: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.6%.
Example 6A reflux condenser tube with a stirrer, a thermometer and a condenser was usedAdding 0.16mol (28.40g) of methyl pentaerythritol silicate and 120ml of diethylene glycol dimethyl ether into a 250ml three-neck flask with an upper opening connected with a drying tube and a hydrogen chloride absorption device, heating to 60 ℃ under the protection of nitrogen, starting to dropwise add 0.05mol (8.78g) of allyl trichlorosilane, after dropwise adding, refluxing and gradually heating to 150 ℃, preserving heat for reaction for 13 hours, adjusting the pH to 6.5-8 by using a triethylamine acid-binding agent, cooling to 25 ℃, filtering, washing by using 70ml of cold water, and drying to obtain white solid allyl caged alcohol silicate, wherein the decomposition temperature is as follows: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 91.4%.
Example 7 in a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.15mol (26.40g) of methyl pentaerythritol silicate, 130ml of ethylene glycol diethyl ether and 0.05mol (8.10g) of allyl trimethoxy silane are added, the temperature is raised to 100 ℃, reflux is started, the reflux is gradually raised to 120 ℃, the temperature is kept for 14h, the temperature at the top of the column is controlled to be not higher than 65 ℃ in the whole process, the separated methanol reaches a theoretical amount, the reaction is stopped, the temperature is cooled to 25 ℃, the filtration is carried out, a filter cake is washed by 70ml of cold water and dried, and white solid allyl trisilicon alcohol silicate is obtained, the decomposition temperature is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 85.2%.
Example 8 in a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.155mol (27.28g) of pentaerythritol methylsilicate, 100ml of tetrachloroethane and 0.05mol (8.10g) of allyltrimethoxysilane are added, the temperature is raised to 100 ℃, reflux is started, the temperature is gradually raised to 130 ℃, the temperature is kept for 15h, the temperature at the top of the column is controlled to be not higher than 65 ℃ in the whole process, the separated methanol reaches the theoretical amount, the reaction is stopped, the temperature is cooled to 25 ℃, the filtration is carried out, a filter cake is washed by 70ml of cold water and dried, and white solid allylsilicic acid trisilicon alcohol ester is obtained, the decomposition temperature is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 88.0%.
Example 9A 250ml three-necked flask equipped with a stirrer, a thermometer and a fractionating device was charged with 0.16mol (28.40g) of pentaerythritol methylsilicate, 100ml of diethylene glycol dimethyl ether and 0.05mol (8.10g) of allyltrimethoxysilane, heated to 100 ℃ to initiate reflux,and (3) refluxing, gradually raising the temperature to 140 ℃, carrying out heat preservation reaction for 16h, controlling the temperature at the top of the tower to be not higher than 65 ℃ in the whole process, enabling the separated methanol to reach the theoretical amount, stopping the reaction, cooling to 25 ℃, filtering, washing a filter cake with 70ml of cold water, and drying to obtain white solid allyl silicic acid trisilicon alcohol ester, wherein the decomposition temperature is as follows: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 91.2%.
Example 10 in a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.165mol (29.04g) of pentaerythritol methylsilicate, 110ml of anisole and 0.05mol (8.10g) of allyltrimethoxysilane are added, the temperature is raised to 100 ℃, reflux is started, the temperature is gradually raised to 150 ℃ in reflux, the temperature is kept for 16h, the temperature at the top of the column is controlled to be not higher than 65 ℃ in the whole process, the separated methanol reaches theoretical amount, the reaction is stopped, the temperature is cooled to 25 ℃, the filtration is carried out, a filter cake is washed by 70ml of cold water and dried, and white solid trisilicon ester of allylsilicate is obtained, the decomposition temperature is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.1%.
Example 11 in a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.17mol (29.29g) of methyl pentaerythritol silicate, 90ml of tetrachloroethane and 0.05mol (8.10g) of allyltrimethoxysilane are added, the temperature is raised to 100 ℃, reflux is started, the temperature is gradually raised to 140 ℃ in reflux, the temperature is kept for 18h, the temperature at the top of the column is controlled to be not higher than 65 ℃ in the whole process, the separated methanol reaches the theoretical amount, the reaction is stopped, the temperature is cooled to 25 ℃, the filtration is carried out, a filter cake is washed by 70ml of cold water and dried, and white solid allylsilicic acid trisilicon alcohol ester is obtained, the decomposition temperature is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.2%.
Example 12 to a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.16mol (28.40g) of pentaerythritol methylsilicate, 120ml of diethylene glycol dimethyl ether and 0.05mol (8.10g) of allyltrimethoxysilane were added, the temperature was raised to 100 ℃ to start reflux, the reflux was gradually raised to 150 ℃ to carry out a heat preservation reaction for 16 hours, the temperature at the top of the column was controlled to be not higher than 65 ℃ in the whole process, the separated methanol was theoretically stopped, the reaction was cooled to 25 ℃, the reaction was stopped, the filtrate was filtered, and 70ml of a filter cake was cooledWashing with water, and drying to obtain white solid allyl silicic acid trisilicon alcohol ester, wherein the decomposition temperature is as follows: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 91.1%.
TABLE 1 preparation examples Main Process parameters
The inventor also applies the prepared product allyl silicic acid trisilicon alcohol ester to 191 unsaturated resin, uniformly mixes the allyl silicic acid trisilicon alcohol ester with the 191 unsaturated resin, methyl ethyl ketone peroxide and cobalt naphthenate according to the proportion in the following table, pours the mixture into a mold paved with glass fiber cloth to prepare a flame-retardant resin sample strip with the length of 15cm, the width of 0.7cm and the thickness of 0.3cm, and tests the flame-retardant performance, wherein the experimental result is shown in table 2.
TABLE 2 oxygen index test results for trisilicon allyl silicate ester in unsaturated resins
From table 2, when the flame retardant additive is not added, the limit oxygen index of the unsaturated resin is 18 percent and the unsaturated resin is combusted when meeting fire, and when the allyl silicon trisilicon alcohol silicate is added to reach 14 percent of the mass of the 191 unsaturated resin system, the limit oxygen index of the flame retardant resin sample strip can reach more than 27 percent of the flame retardant level; when the addition amount of the flame retardant reaches 20% of the mass of the 191 unsaturated resin, the LOI reaches more than 29%, and when the addition amount of the flame retardant reaches 25% of the mass of the 191 unsaturated resin, the LOI reaches more than 31%, the synthesized product contains active groups and is copolymerized with the unsaturated resin to form a body flame-retardant structure, so that the glass fiber reinforced plastic material with excellent performance is obtained, and the allyl silicon trisilicon caged alcohol ester has good flame-retardant performance when being applied to the unsaturated resin.
Claims (5)
1. A reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound is characterized in that the structure of the compound is as follows:
2. the method for preparing the reactive organosilicon flame retardant trisilicon allyl silicate alcohol ester compound as claimed in claim 1, wherein the method comprises:
adding an organic solvent and methyl pentaerythritol silicate into a reactor which is provided with a stirrer, a thermometer and a reflux condenser and is connected with a hydrogen chloride absorption device, heating to 60 ℃, starting to dropwise add allyl trichlorosilane under the protection of nitrogen, heating to 120-150 ℃, carrying out heat preservation reaction for 11-15h, adjusting the pH to 6.5-8 by using an acid-binding agent, cooling to 25 ℃, filtering, washing a filter cake by using cold water with the theoretical mass gram of the product of 2 times volume milliliter, and drying to obtain white solid allyl silicic acid trisilicon ester; the methyl pentaerythrityl silicate is 1-methyl-1-sila-2, 6, 7-trioxa-4-hydroxymethyl bicyclo [2, 2, 2] octane, and the structure of the methyl pentaerythrityl silicate is shown as the following formula:
3. the method for preparing the reactive organosilicon flame retardant trisilicon allyl silicate alcohol ester compound as claimed in claim 1, wherein the method comprises:
adding pentaerythritol methylsilicate, organic solvent and allyltrimethoxysilane into a reactor provided with a stirrer, a thermometer and a fractionating device, heating to 100 ℃, starting reflux, gradually heating to 120-150 ℃ in reflux, keeping the temperature for reaction for 14-18h, controlling the temperature at the top of the tower to be not higher than 65 ℃ in the whole process, leading the separated methanol to reach the theoretical amount, stopping the reaction, cooling to 25 ℃, filtering, washing a filter cake with 60 ml of cold water, and drying to obtain white solid allylsilicic acid trisilicon ester.
4. A process for preparing a reactive organosilicon flame retardant trisilicon allyl silicate alcohol ester compound as claimed in claim 2 or 3, wherein:
the organic solvent is ethylene glycol diethyl ether, tetrachloroethane, diethylene glycol dimethyl ether or anisole, and the volume milliliter number of the organic solvent is 3 to 5 times of the mass gram number of the pentaerythritol methylsilicate.
5. The method for preparing a reactive organosilicon flame retardant trisilicon allyl silicate alcohol ester compound as claimed in claim 2, wherein:
the acid-binding agent is triethylamine, pyridine or N, N-dimethylaniline.
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| CN102153590A (en) * | 2011-01-21 | 2011-08-17 | 华南理工大学 | Caged bicyclic phosphate siloxane flame retardant and preparation method thereof |
| CN104479077A (en) * | 2014-12-09 | 2015-04-01 | 东华大学 | Vinyl silicon-containing cage-shaped phosphate flame retardant and preparation method thereof |
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| CN102146093A (en) * | 2011-02-23 | 2011-08-10 | 苏州科技学院 | Cage-shaped organic silicon flame retardant charring agent and preparation method thereof |
| CN104479077A (en) * | 2014-12-09 | 2015-04-01 | 东华大学 | Vinyl silicon-containing cage-shaped phosphate flame retardant and preparation method thereof |
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